US2017137463A1PendingUtilityA1

Hcv protease inhibitors and uses thereof

Assignee: CELGENE AVILOMICS RES INCPriority: Dec 21, 2007Filed: Jul 5, 2016Published: May 18, 2017
Est. expiryDec 21, 2027(~1.4 yrs left)· nominal 20-yr term from priority
C07K 5/0804C07K 5/0202C12N 9/99C07K 5/081C12N 9/506C07K 5/0812C07K 5/0806C07K 5/0815C07K 5/06165C07K 5/0808C12N 9/96A61K 38/00A61P 31/14C07K 5/0821A61P 31/12
60
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Claims

Abstract

The present invention provides compounds, pharmaceutically acceptable compositions thereof, and methods of using the same.

Claims

exact text as granted — not AI-modified
1 - 47 . (canceled) 
     
     
         48 . A method comprising the step of reacting a compound of formula M: 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1  and R 1′  are independently hydrogen or optionally substituted C 1-6  aliphatic, or R 1  and R 1′  are taken together to form an optionally substituted 3-7 membered carbocyclic ring; 
 R 3  is -L-Y, wherein -L-Y is selected from the following: 
 (l) L is a covalent bond and Y is selected from:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
 
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
         
         (m) L is —C(O)— and Y is selected from:
 (i) C 1-6  alkyl substituted with oxo, halogen, NO 2 , or CN; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
       
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
         
         (n) L is —N(R)C(O)— and Y is selected from:
 (i) C 1-6  alkyl substituted with oxo, halogen, NO 2 , or CN; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
       
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
         
         (o) L is a bivalent C 1-8  saturated, straight or branched, hydrocarbon chain; and Y is selected from:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
       
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
         
         (p) L is a covalent bond, —CH 2 —, —NH—, —C(O)—, —CH 2 NH—, —NHCH 2 —, —NHC(O)—, —NHC(O)CH 2 OC(O)—, —CH 2 NHC(O)—, —NHSO 2 —, —NHSO 2 CH 2 —, or —SO 2 NH—; and Y is selected from:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
       
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
         
         (q) -L-Y is selected from: 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
          or
 each R e  is independently selected from -Q-Z, oxo, NO 2 , halogen, CN, a suitable leaving group, or a C 1-6  aliphatic substituted with oxo, halogen, NO 2 , or CN, wherein:
 Q is a bivalent C 2-6  unsaturated, straight or branched, hydrocarbon chain, wherein one or two methylene units of Q are optionally and independently replaced by —N(R)—, —S—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —SO—, —SO 2 —, —N(R)C(O)—, —C(O)N(R)—, —N(R)SO 2 —, or —SO 2 N(R)—; and 
 Z is hydrogen or C 1-6  aliphatic substituted with oxo, halogen, NO 2 , or CN; or 
 
 
         or R 3  and R 1  are taken together with their intervening atoms to form an optionally substituted saturated or unsaturated 12-18 membered ring having 2-6 heteroatoms independently selected from nitrogen oxygen, or sulfur, wherein the ring formed thereby comprises -L-Y; or 
         R 3  and a ring formed by R 1  and R 1′  are taken together with their intervening atoms to form an optionally substituted saturated or unsaturated 12-18 membered ring having 2-6 heteroatoms independently selected from nitrogen oxygen, or sulfur, wherein the ring formed thereby comprises -L-Y; 
         R 4  is H, —NHC(O)R 5 , —NHC(O)OR 6 , 
       
       
         
           
           
               
               
           
         
          or a natural or unnatural amino acid side-chain group; 
         each R 5  is independently —N(R) 2  or an optionally substituted group selected from C 1-6  aliphatic, a bridged bicyclic, 6-10 membered aryl, 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or 4-7 membered heterocyclyl having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
         R 6  is an optionally substituted group selected from C 1-6  aliphatic, a bridged bicyclic, 6-10 membered aryl, 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or 4-7 membered heterocyclyl having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
         R 7  is an optionally substituted group selected from C 1-6  aliphatic, a bridged bicyclic, 6-10 membered aryl, 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or 4-7 membered heterocyclyl having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
         R z  is 
       
       
         
           
           
               
               
           
         
          or R 4  and R z  are taken together with their intervening atoms to form an optionally substituted, saturated or unsaturated 16-22 membered ring having 2-6 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
         each occurrence of R y  is independently selected from halogen, —OR ◯ , —CN, —NO 2 , —N(R ◯ ) 2 , or optionally substituted C 1-4  aliphatic;
 each R ◯  is independently optionally substituted C 1-6  aliphatic; 
 
         m is an integer from 0 to 4, inclusive; 
         s is an integer from 0 to 4, inclusive; 
         t is an integer from 0 to 4, inclusive; and 
         wherein the sum of s and t is non-zero; 
       
       with a sulfonamide of formula E: 
       
         
           
           
               
               
           
         
       
       wherein
 R 2  is —N(R) 2  or an optionally substituted group selected from C 3-7  cycloalkyl, a bridged bicyclic, 6-10 membered aryl, 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or 4-7 membered heterocyclyl having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
 each R is independently hydrogen, optionally substituted C 1-6  aliphatic, or:
 two R on the same nitrogen atom are taken together with the nitrogen to form a 4-7 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 
 
 
       to provide a compound of formula I: 
       
         
           
           
               
               
           
         
       
     
     
         49 . The method of  claim 48 , further comprising the step of hydrolyzing an ester of formula L: 
       
         
           
           
               
               
           
         
       
       to provide a compound of formula M: 
       
         
           
           
               
               
           
         
       
     
     
         50 . The method of  claim 49 , further comprising the step of deprotecting a compound of formula K: 
       
         
           
           
               
               
           
         
         wherein -PG is a suitable amino protecting group; 
       
       to provide a compound of formula L: 
       
         
           
           
               
               
           
         
       
       wherein R 4  is —NHC(O)R 5 , —NHC(O)OR 6 , or 
       
         
           
           
               
               
           
         
       
     
     
         51 . The method of  claim 50 , further comprising the step of reacting an amino acid of formula H: 
       
         
           
           
               
               
           
         
       
       with an amine of formula J: 
       
         
           
           
               
               
           
         
       
       to provide a compound of formula K: 
       
         
           
           
               
               
           
         
       
     
     
         52 . The method of  claim 51 , further comprising the step of deprotecting a compound of formula C: 
       
         
           
           
               
               
           
         
         wherein -PG is a suitable amino protecting group; 
       
       to provide a compound of formula J: 
       
         
           
           
               
               
           
         
       
     
     
         53 . The method of  claim 49 , further comprising the step of performing ring closing metathesis to provide an ester of formula L: 
       
         
           
           
               
               
           
         
         wherein R 4  and R z  are taken together with their intervening atoms to form an optionally substituted, saturated or unsaturated 16-22 membered ring having 2-6 heteroatoms independently selected from nitrogen, oxygen, or sulfur. 
       
     
     
         54 . The method according to  claim 48 , wherein:
 (l) L is a covalent bond and Y is selected from:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
   
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
       
     
     
         55 . The method according to  claim 48 , wherein
 (m) L is —C(O)— and Y is selected from:
 (i) C 1-6  alkyl substituted with oxo, halogen, NO 2 , or CN; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
   
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
           or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
       
     
     
         56 . The method according to  claim 48 , wherein (n) L is —N(R)C(O)— and Y is selected from:
 (i) C 1-6  alkyl substituted with oxo, halogen, NO 2 , or CN; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
 
       
         
           
           
               
               
           
         
          or 
         (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
         (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
         (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
         (x) 
       
       
         
           
           
               
               
           
         
          or 
         (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
         (xii) 
       
       
         
           
           
               
               
           
         
          or 
         (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
         (xiv) 
       
       
         
           
           
               
               
           
         
          or 
         (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
         (xvi) 
       
       
         
           
           
               
               
           
         
          or 
         (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
         (xviii) 
       
       
         
           
           
               
               
           
         
       
     
     
         57 . The method according to  claim 48 , wherein
 (o) L is a bivalent C 1-8  saturated, straight or branched, hydrocarbon chain; and Y is selected from:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
   
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
       
     
     
         58 . The method according to  claim 48 , wherein:
 L is a covalent bond, —C(O)—, —N(R)C(O)—, —NH—, —CH 2 NH—, —NHCH 2 —, —NHC(O)CH 2 OC(O)—, —CH 2 NHC(O)—, —NHSO 2 —, —NHSO 2 CH 2 —, —SO 2 NH—, or a bivalent C 1-8  saturated, straight or branched, hydrocarbon chain; and   Y is selected from the following:
 (i) —CH 2 F, —CH 2 Cl, —CH 2 CN, or —CH 2 NO 2 ; or 
 (iii) C 2-6  alkynyl optionally substituted with oxo, halogen, NO 2 , or CN; or 
 (iv) a saturated 3-4 membered heterocyclic ring having 1 heteroatom selected from oxygen or nitrogen wherein said ring is substituted with 1-2 R e  groups; or 
 (v) a saturated 5-6 membered heterocyclic ring having 1-2 heteroatoms selected from oxygen or nitrogen wherein said ring is substituted with 1-4 R e  groups; or 
 (vi) 
   
       
         
           
           
               
               
           
         
         
            or 
           (vii) a saturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (viii) a partially unsaturated 3-6 membered monocyclic ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (ix) a partially unsaturated 3-6 membered carbocyclic ring, wherein said ring is substituted with 1-4 R e  groups; or 
           (x) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xi) a partially unsaturated 4-6 membered heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xii) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xiii) a 6-membered aromatic ring having 0-2 nitrogens wherein said ring is substituted with 1-4 R e  groups; or 
           (xiv) 
         
       
       
         
           
           
               
               
           
         
         
            or 
           (xv) a 5-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-3 R e  groups; or 
           (xvi) 
         
       
       
         
           
           
               
               
           
         
         
           (xvii) an 8-10 membered bicyclic, saturated, partially unsaturated, or aryl ring having 0-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein said ring is substituted with 1-4 R e  groups; or 
           (xviii) 
         
       
       
         
           
           
               
               
           
         
       
     
     
         59 . The method according to  claim 58 , wherein L is a covalent bond, —CH 2 —, —NH—, —C(O)—, —CH 2 NH—, —NHCH 2 —, —NHC(O)—, —NHC(O)CH 2 OC(O)—, —CH 2 NHC(O)—, —NHSO 2 —, —NHSO 2 CH 2 —, or —SO 2 NH—. 
     
     
         60 . The method according to  claim 48 , wherein Y is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein each R e  is independently selected from halogen. 
     
     
         61 . The method according to  claim 48 , wherein R 3  is selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein each R e  is independently a suitable leaving group, NO 2 , CN, or oxo. 
     
     
         62 . The method of  claim 49 , wherein the R group of the depicted ester moiety of formula L is C 1-6  aliphatic. 
     
     
         63 . The method of  claim 50 , wherein the step of deprotection comprises a suitable base. 
     
     
         64 . The method of  claim 63 , wherein a suitable base is an alkaline metal, alkaline earth metal hydroxide, or combination thereof. 
     
     
         65 . The method of  claim 50 , further comprising a neutralizing step following hydrolysis. 
     
     
         66 . The method of  claim 52 , wherein the protecting group is a Boc group. 
     
     
         67 . The method of  claim 52 , wherein the protecting group is removed under acid-catalyzed conditions.

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