US2008166362A1PendingUtilityA1

New effector conjugates, process for their production and their pharmaceutical use

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Assignee: BERGER MARKUSPriority: Jul 31, 2002Filed: Dec 11, 2007Published: Jul 10, 2008
Est. expiryJul 31, 2022(expired)· nominal 20-yr term from priority
A61P 35/00A61P 25/00A61P 3/00A61P 29/00A61P 19/00C07D 405/06C07D 417/04A61K 47/6809C07D 493/04A61K 47/6851C07D 413/04C07D 417/06C07D 413/06C07D 417/14
60
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Claims

Abstract

Conjugates of epothilones and epothilone derivatives (as effectors) with suitable biomolecules (as recognition units) are described. Their production is carried out by the effectors being reacted with suitable linkers, and the compounds that are produced are conjugated to the recognition units. The pharmaceutical use of the conjugates for treating proliferative or angiogenesis-associated processes is described.

Claims

exact text as granted — not AI-modified
1 - 28 . (canceled) 
     
     
         29 . An effector recognition unit conjugate of formula (I), 
       
         
           
           
               
               
           
         
       
       in which
 R 1a , R 1b , independently of one another, are hydrogen, C 1 -C 10  alkyl, aryl, aralkyl, or together a —CH 2 ) m  group, in which m is 2 to 5, 
 R 2a , R 2b , independently of one another, are hydrogen, C 1 -C 10  alkyl, aryl, aralkyl, or together a —(CH 2 ) n  group, in which n is 2 to 5, or C 2 -C 10  alkenyl, or C 2 -C 10  alkynyl, 
 R 3  is hydrogen, C 1 -C 10  alkyl, aryl or aralkyl, and 
 R 4a , R 4b , independently of one another, are hydrogen, C 1 -C 10  alkyl, aryl, aralkyl, or together a —CH 2 ) p  group, in which p is 2 to 5, 
 R 5  is hydrogen, C 1 -C 10  alkyl, aryl, aralkyl, CO 2 H, CO 2 alkyl, CH 2 OH, CH 2 Oalkyl, CH 2 Oacyl, CN, CH 2 NH 2 , CH 2 N(alkyl, acyl) 1,2 , or CH 2 Hal, 
 Hal is a halogen atom, 
 R 6 , R 7  in each case are hydrogen, or together an additional bond, or together an oxygen atom, or together an NH group, or together an N-alkyl group, or together a CH 2  group, and 
 G is an oxygen atom or CH 2 , 
 D-E is a group H 2 C—CH 2 , HC═CH, C≡C, CH(OH)—CH(OH), CH(OH)—CH 2 , CH 2 —CH(OH), 
 
       
         
           
           
               
               
           
         
       
       O—CH 2 , or, if G represents a CH 2  group, D-E is CH 2 —O,
 W is a group C(═X)R 8 , or a bicyclic or tricyclic aromatic or heteroaromatic radical, 
 L 3  is hydrogen, or, if a radical in W contains a hydroxyl group, forms a group O-L 4  with the latter, or, if a radical in W contains an amino group, forms a group 
 NR 25 -L 4  with the latter, 
 R 25  is hydrogen or C 1 -C 10  alkyl, 
 X is an oxygen atom, or two OR 20  groups, or a C 2 -C 10  alkylenedioxy group that may be straight or branched, or H and OR 9 , or a CR 10 R 11  group, 
 R 8  is hydrogen, C 1 -C 10  alkyl, aryl, aralkyl, halogen or CN, and 
 R 9  is hydrogen or a protective group PG X , 
 R 10 , R 11 , in each case independently of one another, are hydrogen, C 1 -C 20  alkyl, aryl, aralkyl, or together with a methylene carbon atom form a 5- to 7-membered carbocyclic ring, 
 Z can represent oxygen or H and OR 12 , 
 R 12  can represent hydrogen or a protective group PG Z , 
 A-Y can represent a group O—C(═O), O—CH 2 , CH 2 —C(═O), NR 21 —C(═O) or NR 21 —SO 2 , 
 R 20  can represent C 1 -C 20  alkyl, 
 R 21  can represent a hydrogen atom or C 1 -C 10  alkyl, 
 PG X , PG Y , and PG Z  can represent a protective group PG, and 
 L 1 , L 2 , and L 4 , independently of one another, can represent hydrogen, a group C(═O)Cl, a group C(═S)Cl, a group PGY or a linker of general formula (III) or (IV);
 provided that at least one substituent L 1 , L 2  or L 4  represents a linker of general formula (III) or (IV); 
 
 the linker of general formula (III) has the following structure, 
 
       
         
           
           
               
               
           
         
       
       in which
 T can represent oxygen or sulfur, 
 U can represent oxygen, CHR 22 , CHR 22 —NR 23 —C(═O)—, O—C(═O)—CHR 22 —NR 23 —C(═O)—, O—C(═O)—CHR 22 —NR 23 —C(═S)—, CHR 22 —NR 23 —C(═S)— or NR 24a , 
 o can represent 0 to 15, 
 V can represent a bond, aryl, a group 
 
       
         
           
           
               
               
           
         
         
           or a group 
         
       
       
         
           
           
               
               
           
         
         s can represent 0 to 4, 
         Q can represent a bond, O—C(═O)—NR 24c , O—C(═S)—NR 24c , 
       
       
         
           
           
               
               
           
         
         R 22  can represent hydrogen, C 1 -C 10  alkyl, aryl or aralkyl, 
         R 23  can represent hydrogen or C 1 -C 10  alkyl, 
         R 24a , R 24b , and R 24c , independently of one another, can represent hydrogen or 
         C 1 -C 10  alkyl, 
         q can represent 0 to 15, 
         FG 1  can represent C 1 -C 10  alkyl-S 3 , 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
          or CO 2 H; and 
         the linker of general formula (IV) has the following structure, 
       
       
         
           
           
               
               
           
         
       
       in which
 T can represent oxygen or sulfur, 
 W1, W2 are the same or different and can represent oxygen or NR 24a , 
 o can represent 0 to 5, 
 R 24a  can represent hydrogen or C 1 -C 10  alkyl, 
 R 27  can represent halogen, CN, NO 2 , CO 2 R 28 , or OR 28 , 
 R 28  can represent hydrogen, C 1 -C 10  alkyl, aryl or aralkyl, 
 q can represent 0 to 5, 
 U can represent oxygen, CHR 22 , CHR 22 —NR 23 —C(═O)—, CHR 22 —NR 23 —C(═S)— or 
 C 1 -C 20  alkyl, 
 R 22  can represent hydrogen, C 1 -C 10  alkyl, aryl or aralkyl, 
 R 23  can represent hydrogen or C 1 -C 10  alkyl, 
 r can represent 0 to 20, 
 FG 1  can represent C 1 -C 10  alkyl-S 3 , 
 
       
         
           
           
               
               
           
         
          or CO 2 H, 
       
       and wherein 
       at least one group FG 1  is not as defined above, but instead is a group FG 2a  or FG 2b , wherein 
       FG 2a  is —S—S—, 
       
         
           
           
               
               
           
         
       
       FG 2 b is —CONH—; 
       wherein 
       a recognition unit is conjugated via a sulfur atom with group FG 2 a or via an amide function with group FG 2 b ; 
       and wherein the recognition unit is selected from peptides, soluble receptors, cytokines, lymphokines, aptamers, spiegelmers, recombinant proteins, new framework structures, monoclonal antibodies and fragments of monoclonal antibodies; 
       or 
       a single isomer or a mixture of different isomers or a pharmaceutically acceptable salt thereof. 
     
     
         30 . An effector recognition unit conjugate according to  claim 29 , wherein the conjugate contains more than one recognition unit, and wherein the recognition units are identical. 
     
     
         31 . An effector recognition unit conjugate according to  claim 29 , wherein the recognition unit is an antibody, or an antigen-binding fragment thereof, which is specific for an antigen that is selected from OC 125, OC 133, OMI, Mo vl, Mo v2, 3C2, 4C7, ID3, DU-PAN-2, F 36/22, 4F7/7A10, OV-TL3, B72.3, DF3, 2C8/2F7, MF 116, Mov18, CEA 1′-H5, CA 19-9, (1116NS19-9), H17-E2, 791T/36, NDOG2, H317, 4D5, 3H4, 7C2, 6E9, 2C4, 7F3, 2H1, 3E8, 5B8, 7D3, SB8, HMFG2, 3.14.A3, DF3, NCRC-11, 3C6F9, MBE6, CLNH 5 , MAC 40/43, EMA, HMFG1 HFMG2, 3.15.C3, M3, M8, M24, M18,67-D-11, D547Sp, D75P3, H222, Anti EGF, LR-3, TA1, H59, 10-3D-2, HmAB1,2, MBR 1,2,3, 24-17-1, 24-17-2 (3E1-2), F36/22.M7/105, C11, G3, H7, B6-2, BI-1, Cam 17-1, SM3, SM4, C-Mul (566), 4D53H4, 7C2, 6E9, 2C4, 7F3, 2H11, 3E8, 5B8, 7D3, 5B8, OC 125, MO v2, DU-PAN-2, 4F7/7A10, DF3, B72-3, cccccCEA 11, H17-E2, 3-14-A3, F023C5, B72-3, (17-1A) 1038-17-1A, C017-1A, ZCE-025, AB2, HT-29-15, 250-30.6, 44×14, A7, GA73-3, 791T/36, 28A32, 28.19.8, X MMCO-791, DU-PAN-2, ID3, CEA, 1-H5, 2C8/2F7, CA-19-9 (1116NS19-9), PR5C5, PR4D2, PR4D1, 4-1, 8-2 M17, 96-5, 118-1, 133-2, (113-2), L1, L10, R10 (R19), 112, K5, 6-1, R24, 5-1, 225.28S, 465.12S, 9-2-27, F11, 376.96S, 465.12S, 15-75, 15-95, Me1-14, Me1-12, Me3-TB7, 225.28SD, 763.24TS, 705F6, 436910, M148, ID3, DU-PAN-2, OV-TL3, B72-3, CEA 1-H5, 3-14-A3, C COL1, CA-19-9, 116NS19-9) and CA50, OC125, 4D5, 3H4, 7C2, 6E9, 2C4, 7F3, 2H11, 3E8, 5B8, 7D3, SB8, MO v2, B72-3, DU-PAN-2, CEA 11-H5, MUG 8-22, MUC2-63, MUC2-39, MUG 7-39, PAb 240, PAb 246, PAb 1801, ERIC-1, M148, FMH25, 6-1, CA1, 3F8, 4F7/7A10, 2C8/2F7, CEA, 11-H5, 2H8, 10G6, CD19, CD20, CD40, CD22, CD25, CD5, CD52, CD10, CD2, CD7, CD33, CD38, CD40, CD72, CD4, CD21, CD37, CD30, VCAM, CD31, ELAM, endoglin, VEGFR1/II, α v β 3  Tie½, TES23 (CD44ex6), phosphatidylserine, PSMA, VEGFR/VEGF complex and ED-B-fibronectin. 
     
     
         32 . A method for preparing an effector recognition unit conjugate according to  claim 29  comprising reacting an effector conjugate of formula (I) with at least one recognition unit selected from peptides, soluble receptors, cytokines, lymphokines, aptamers, spiegelmers, recombinant proteins, new framework structures, monoclonal antibodies and fragments of monoclonal antibodies. 
     
     
         33 . A method according to  claim 32 , wherein the effector conjugate of formula (I), is prepared by reacting
 a compound of formula (I), wherein at least one substituent L 1 , L 2  or L 4  represent a linker of formula (III) or (IV), and at least one substituent L 1 , L 2  or L 4  represents hydrogen, a group C(═O)Cl, or a group C(═S)Cl,   with a linker that is selected from a linker of formula (III 1 ), (III 2 ), (III 3 ), (IV 1 ), (IV 2 ) and (IV 3 ),
   RG 1 -(CH 2 ) o —V—(CH 2 ) q —FG 1   III 1 , 
   
       in which 
       RG 1  is an O═C═N group or an S═C═N group, 
       o is 0 to 15, 
       V is a bond, aryl, a group 
       
         
           
           
               
               
           
         
       
       or a group 
       
         
           
           
               
               
           
         
       
       q is Oto 15, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H;
   RG 2 -(CH 2 ) o —V—(CH 2 ) q FG 1   III 2 , 
 
       in which 
       RG2 is a Hal-C(=T)-CHR 22  group, or a Hal-C(=T)-CHR 22 —NR 23 —C(=T) group, or an R 26 —C(═O)—O—C(=T)-CHR 22  group, or an R 26 —C(═O)—O—C(=T)-CHR 22 —NR 23 —C(=T) group, wherein R 26  is C 1 -C 10  alkyl, aryl, or aralkyl, 
       o is Oto 15, 
       V is a bond, aryl, a group 
       
         
           
           
               
               
           
         
       
       or a group 
       
         
           
           
               
               
           
         
       
       q is 0 to 15, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H;
   RG 3 -(CH 2 ) o —V—(CH 2 ) q —FG 1   III 3 , 
 
       in which 
       RG 3  is an OH group, or an NHR 24a  group, or a COOH group, 
       o is Oto 15, 
       V is a bond, aryl, a group 
       
         
           
           
               
               
           
         
       
       or a group 
       
         
           
           
               
               
           
         
       
       q is 0 to 15, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H; 
       with the proviso that the compound I-(4-amino-phenyl)-pyrrole-2,5-dione is not included; 
       
         
           
           
               
               
           
         
       
       in which 
       RG 1  is an O═C═N group or an S═C═N group, 
       W 2  is oxygen or NR 24a , 
       o is 0 to 5, 
       R 27  is halogen, CN, NO 2 , CO 2 R 28 , or OR 28 , 
       q is 0 to 5, 
       U is oxygen, CHR 22 , CHR 22 —NR 23 —C(═O)—CHR 22 —NR 23 OC(S)C 
       r is 0 to 20, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H, 
       
         
           
           
               
               
           
         
       
       in which 
       RG 2  is a Hal-C(=T)-CHR 22  group, or a Hal-C(=T)-CHR 22 —NR 23 —C(=T) group, or an R 26 —C(═O)—O—C(=T)-CHR 22  group, or an R 26 —C(═O)—O—C(=T)-CHR 22 —NR 23 —C(=T) group, wherein R 26  is C 1 -C 10  alkyl, aryl, or aralkyl, 
       T is oxygen or sulfur, 
       W 2  is oxygen or NR 14a , 
       o is 0 to 5, 
       R 27  is halogen, CN, NO 2 , CO 2 R 28 , or OR 28 , 
       q is 0 to 5, 
       U is oxygen, CHR 22 , CHR 22 —NR 23 —C(═O)—, CHR 22 —NR 23 —C(═S)— or C 1 -C 20  alkyl, 
       R 22  is hydrogen, C 1 -C 10  alkyl, aryl or aralkyl, 
       R 23  is hydrogen or C 1 -C 10  alkyl, 
       r is 0 to 20, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H, 
       
         
           
           
               
               
           
         
       
       in which 
       RG 3  is an OH group or an NHR 24a  group or a COOH group, 
       W 2  is oxygen or NR 24a , 
       o is Oto 5, 
       R 24a  is hydrogen or C 1 -C 10  alkyl, 
       R 27  is halogen, CN, NO 2 , CO 2 R 28 , or OR 28 , 
       q is 0 to 5, 
       U is oxygen, CHR 22 , CHR 22 —NR 23 C(═O)—, CHR 22 —NR 23 —C(═S)— or C 1 -C 20  alkyl, 
       r is 0 to 20, 
       FG 1  is C 1 -C 10  alkyl-S 3 , 
       
         
           
           
               
               
           
         
       
       or CO 2 H. 
     
     
         34 . A method according to  claim 33 , wherein in the effector conjugate of formula (I) at least one substituent L 1 , L 2  or L 4  represent a linker of formula (III) or (IV), and at least one substituent L 1 , L 2  or L 4  represents hydrogen, a group C(═O)Cl, or a group C(═S)Cl. 
     
     
         35 . A pharmaceutical composition comprising an effector recognition unit conjugate according to  claim 29  and a pharmaceutically acceptable carrier. 
     
     
         36 . A method for treating a disease that is associated with proliferative processes comprising administering to a patient in need thereof an effective amount of a pharmaceutical composition according to  claim 35 . 
     
     
         37 . A method for treating a tumor, an inflammatory disease, a neurodegenerative disease, an angiogenesis-associated disease, multiple sclerosis, Alzheimer's disease, or rheumatoid arthritis comprising administering to a patient in need thereof an effective amount of a pharmaceutical composition according to  claim 35 . 
     
     
         38 . A method for treating multiple sclerosis, Alzheimer's disease, or rheumatoid arthritis comprising administering to a patient in need thereof an effective amount of a pharmaceutical composition according to  claim 35 . 
     
     
         39 . A method for treating a tumor comprising administering to a patient in need thereof an effective amount of a pharmaceutical composition according to  claim 35 . 
     
     
         40 . An effector recognition unit conjugate according to  claim 29 , wherein the effector element is 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-1-methyl-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-methyl-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-methyl-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-11-methyl-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl) 1-methyl-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-methyl-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7, 11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-methyl-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-11-methyl-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-fluoro-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-1-fluoro-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-fluoro-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-fluoro-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-fluoro-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-1-fluoro-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-chloro-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-1-chloro-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-chloro-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-chloro-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1. O]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-chloro-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-1-chloro-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-fluoro-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl) 1-fluoro-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-fluoro-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-fluoro-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-fluoro-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-1-fluoro-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-chloro-2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-1-chloro-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-thiazol-4-yl)-1-chloro-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-chloro-2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-1-chloro-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-1-chloro-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-methyl-2-(2-pyridyl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,1,1-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-methyl-2-(2-pyridyl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-methyl-2-(2-pyridyl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-methyl-2-(2-pyridylvinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-fluoro-2-(2-pyridyl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-fluoro-2-(2-pyridyl)vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-chloro-2-(2-pyridylvinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-chloro-2-(2-pyridylvinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-fluoro-2-(2-pyridylvinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,1,1-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-fluoro-2-(2-pyridyl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-chloro-2-(2-pyridyl)vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-chloro-2-(2-pyridylvinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-methyl-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-methyl-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-methyl-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-methyl-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-methyl-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-methyl-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-methyl-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-methyl-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-fluoro-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-fluoro-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-fluoro-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-fluoro-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-fluoro-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-fluoro-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[1-chloro-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-chloro-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-chloro-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[1-chloro-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-chloro-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-chloro-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-fluoro-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-fluoro-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-fluoro-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-fluoro-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione;
 (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-fluoro-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-fluoro-vinyl]-7,11-dihydroxy 10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[1-chloro-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-oxazol-4-yl)-1-chloro-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(Z))-16-[2-(2-Aminomethyl-oxazol-4-yl)-1-chloro-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,1,1-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[1-chloro-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-oxazol-4-yl)-1-chloro-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (1S,3S(Z),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-oxazol-4-yl)-1-chloro-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]hepta-decane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-vinyl]-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-thiazol-4-yl)-vinyl]-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,1S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-vinyl]-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-vinyl]-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[2-(2-methyl-thiazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-[2-(2-hydroxymethyl-thiazol-4-yl)-vinyl]-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-16-[2-(2-Aminomethyl-thiazol-4-yl)-vinyl]-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[2-(2-methyl-thiazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-[2-(2-hydroxymethyl-thiazol-4-yl)-vinyl]-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-3-[2-(2-Aminomethyl-thiazol-4-yl)-vinyl]-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[2-(2-pyridyl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[2-(2-pyridylvinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-[2-(2-pyridyl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-[2-(2-pyridyl)vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,1,1-Dihydroxy-8,8,10,12,16-pentamethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-propyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-propyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-propyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-propyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-propyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-propyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-butyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-butyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-butyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-butyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-butyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-butyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-prop-2-inyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-prop-2-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-prop-2-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-prop-2-inyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-prop-2-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-prop-2-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-but-3-enyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-but-3-enyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-but-3-enyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-but-3-enyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-but-3-enyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-but-3-enyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-but-3-inyl-5,5,9,13-tetramethyl-16-(2-methyl-benzothiazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzothiazol-5-yl)-7-but-3-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzothiazol-5-yl)-4,8-dihydroxy-7-but-3-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-but-3-inyl-8,8,12,16-tetramethyl-3-(2-methyl-benzothiazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzothiazol-5-yl)-10-but-3-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzothiazol-5-yl)-7,11-dihydroxy-10-but-3-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-5,5,7,9,13-pentamethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-8,8,10,12,16-pentamethyl-4,17-dioxa-bicyclo[114.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-ethyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-ethyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-ethyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-ethyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-propyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-propyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)—I 6-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-propyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R, I S,12S,16R)-7,11-Dihydroxy-10-propyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-propyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-propyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-butyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-butyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-butyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-butyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1. O]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-butyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1. O]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-butyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1. O]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-prop-2-inyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-prop-2-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-prop-2-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-prop-2-inyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-prop-2-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-prop-2-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-but-3-enyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-but-3-enyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-but-3-enyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-but-3-enyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-but-3-enyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-but-3-enyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-7-but-3-inyl-5,5,9,13-tetramethyl-16-(2-methyl-benzoxazol-5-yl)-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)-4,8-Dihydroxy-16-(2-hydroxymethyl-benzoxazol-5-yl)-7-but-3-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (4S,7R,8S,9S,13Z,16S)— 16-(2-Aminomethyl-benzoxazol-5-yl)-4,8-dihydroxy-7-but-3-inyl-5,5,9,13-tetramethyl-oxacyclohexadec-13-ene-2,6-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-but-3-inyl-8,8,12,16-tetramethyl-3-(2-methyl-benzoxazol-5-yl)-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-3-(2-hydroxymethyl-benzoxazol-5-yl)-10-but-3-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione; 
       (1S,3S,7S,10R,11S,12S,16R)-3-(2-Aminomethyl-benzoxazol-5-yl)-7,11-dihydroxy-10-but-3-inyl-8,8,12,16-tetramethyl-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione, wherein the hydrogen atoms in the above-mentioned effector elements are replaced in the positions indicated in formula (I) by radicals L 1 -L 3 . 
     
     
         41 . An effector recognition unit conjugate according to  claim 29 , wherein in the effector element
 A-Y represents O—C(═O) or NR 21 —C(═O),   D-E represents an H 2 C—CH 2  group,   G represents a CH 2  group,   z represents an oxygen atom,   R 1a , R 1b  in each case represent C 1 -C 10  alkyl or together a —(CH 2 ) p  group with p equal to 2 or 3 or 4,   R 2a , R 2b , independently of one another, represent hydrogen, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, or C 2 -C 10  alkynyl,   R 3  represents hydrogen,   R 4a , R 4b , independently of one another, represent hydrogen or C 1 -C 10  alkyl;   R 5  represents hydrogen, or C 1 -C 4  alkyl or CH 2 OH or CH 2 NH 2  or CH 2 N(alkyl, acyl) 1,2  or CH 2 Hal,   R 6  and R 7  together represent an additional bond or together an NH group, or together an N-alkyl group, or together a CH 2  group, or together an oxygen atom,   W represents a group C(═X)R 8  or a 2-methylbenzothiazol-5-yl radical or a 2-methylbenzoxazol-5-yl radical or a quinolin-7-yl radical or a 2-aminomethylbenzothiazol-5-yl radical or a 2-hydroxymethylbenzothiazol-5-yl radical or a 2-aminomethyl-benzoxazol-5-yl radical or a 2-hydroxymethylbenzoxazol-5-yl radical,   X represents a CR 10 R 11  group,   R 8  represents hydrogen or C 1 -C 4  alkyl or a fluorine atom or a chlorine atom or a bromine atom,   R 10 /R 11  represent hydrogen/2-methylthiazol-4-yl or hydrogen/2-pyridyl or hydrogen/2-methyloxazol-4-yl or hydrogen/2-aminomethylthiazol-4-yl or hydrogen/2-aminomethyloxazol-4-yl or hydrogen/2-hydroxymethylthiazol-4-yl or hydrogen/2-hydroxymethyloxazol-4-yl.   
     
     
         42 . An effector recognition unit conjugate according to  claim 29 , wherein in the effector element the linker is a compound of formula (III), wherein
 V represents a bond or an aryl radical,   o is zero, and   T is an oxygen atom.   
     
     
         43 . An effector recognition unit conjugate according to  claim 29 , wherein in the effector element the linker is a compound of formula (III), wherein
 V represents a bond or an aryl radical or a group   
       
         
           
           
               
               
           
         
         is 0 to 4, and 
         Q is a bond or a group 
       
       
         
           
           
               
               
           
         
       
     
     
         44 . An effector recognition unit conjugate according to  claim 29 , wherein in the effector element the linker is a compound of formula (III), wherein
 V is a bond or a group   
       
         
           
           
               
               
           
         
         Q is a bond or a group 
       
       
         
           
           
               
               
           
         
         o is 0, 2 or 3, 
         s is 1, and 
         T is an oxygen atom. 
       
     
     
         45 . An effector recognition unit conjugate according to  claim 29 , wherein in the effector element the linker is a compound of formula (IV), wherein
 o is 0 to 4, and   q is 0 to 3.

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