Hydroxide-Catalyzed Formation Of Silicon-Oxygen Bonds By Dehydrogenative Coupling Of Hydrosilanes And Alcohols

Abstract

The present disclosure is directed to methods for dehydrogenatively coupled hydrosilanes and alcohols, the methods comprising contacting an organic substrate having at least one organic alcohol moiety with a mixture of at least one hydrosilane and sodium and/or potassium hydroxide, the contacting resulting in the formation of a dehydrogenatively coupled silyl ether. The disclosure further described associated compositions and methods of using the formed products.

What is claimed: 
     
         1 . A compound of formula: 
       
         
           
           
               
               
           
         
         wherein
 X is H or OH; 
 p is 0 or 1; 
 each R B  is independently a tertiary alkyl; and 
 (Het)Aryl is an optionally substituted phenyl, naphthyl, or 5- or 6-membered heteroaryl. 
 
       
     
     
         2 . The compound according to  claim 1 , wherein X is H. 
     
     
         3 . The compound according to  claim 1 , wherein X is OH. 
     
     
         4 . The compound according to  claim 1 , wherein p is 0. 
     
     
         5 . The compound according to  claim 1 , wherein p is 1. 
     
     
         6 . The compound according to  claim 1 , wherein at least one R B  is tert-butyl. 
     
     
         7 . The compound according to  claim 1 , wherein the optional substituent is independently halo, optionally protected hydroxyl, sulfhydryl, C 1 -C 24  alkoxy, C 2 -C 24  alkenyloxy, C 2 -C 24  alkynyloxy, C 5 -C 24  aryloxy, C 6 -C 24  aralkyloxy, C 6 -C 24  alkaryloxy, C 1 -C 24  alkylcarbonyl (—CO-alkyl), C 6 -C 24  arylcarbonyl (—CO-aryl)), C 2 -C 24  alkylcarbonyloxy (—O—CO-alkyl), C 6 -C 24  arylcarbonyloxy (—O—CO-aryl)), C 2 -C 24  alkoxycarbonyl ((CO)—O-alkyl), C 6 -C 24  aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)-X where X is halo), C 2 -C 24  alkylcarbonato (—O—(CO)—O-alkyl), C 6 -C 24  arylcarbonato (—O—(CO)—O-aryl), optionally protected carboxy (—COOH), carboxylato (—COO—), optionally protected carbamoyl (—(CO)—NH 2 ), mono-(C 1 -C 24  alkyl)-substituted carbamoyl (—(CO)NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  alkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 1 -C 24  haloalkyl)-substituted carbamoyl (—(CO)—NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  haloalkyl)-substituted carbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 5 -C 24  aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C 5 -C 24  aryl)substituted carbamoyl (—(CO)—N(C 5 -C 24  aryl) 2 ), di-N—(C 1 -C 24  alkyl), N—(C 5 -C 24  aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH 2 ), mono-(C 1 -C 24  alkyl)-substituted thiocarbamoyl (—(CO)—NH(C 1 -C 24  alkyl)), di-(C 1 -C 24  alkyl)-substituted thiocarbamoyl (—(CO)—N(C 1 -C 24  alkyl) 2 ), mono-(C 5 -C 24  aryl)substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C 5 -C 24  aryl)-substituted thiocarbamoyl (—(CO)—N(C 5 -C 24  aryl) 2 ), di-N—(C 1 -C 24  alkyl), N—(C 5 -C 24  aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH 2 ), cyano(-C≡N), cyanato (—O—C═N), thiocyanato (—S—C═N), formyl (—(CO)—H), thioformyl (—(CS)—H), optionally protected amino (—NH 2 ), optionally protected mono-(C 1 -C 24  alkyl)-substituted amino, di-(C 1 -C 24  alkyl)-substituted amino, optionally protected mono-(C 5 -C 24  aryl)substituted amino, di-(C 5 -C 24  aryl)-substituted amino, C 1 -C 24  alkylamido (—NH—(CO)-alkyl), C 6 -C 24  arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C 1 -C 24  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, or C 6 -C 24  aralkyl), C 2 -C 20  alkylimino (—CR═N(alkyl), where R=hydrogen, C 1 -C 24  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, or C 6 -C 24  aralkyl), arylimino (—CR═N(aryl), where R=hydrogen, C 1 -C 20  alkyl, C 5 -C 24  aryl, C 6 -C 24  alkaryl, C 6 -C 24  aralkyl, etc.), nitro (—NO 2 ), nitroso (—NO), optionally protected sulfo (—SO 2 OH), sulfonate(SO 2 O—), C 1 -C 24  alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C 5 -C 24  arylsulfanyl (—S-aryl; also termed “arylthio”), C 1 -C 24  alkylsulfinyl (—(SO)-alkyl), C 5 -C 24  arylsulfinyl (—(SO)-aryl), C 1 -C 24  alkylsulfonyl (—SO 2 -alkyl), C 1 -C 24  monoalkylaminosulfonyl-SO 2 —N(H) alkyl), C 1 -C 24  dialkylaminosulfonyl-SO 2 —N(alkyl) 2 , C 5 -C 24  arylsulfonyl (—SO 2 -aryl), boryl (—BH 2 ), borono (—B(OH) 2 ), boronato (—B(OR) 2  where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH) 2 ), phosphonato (—P(O)(O) 2 ), phosphinato (P(O)(O—)), phospho (—PO 2 ), phosphine (—PH 2 ), optionally substituted C 1 -C 24  alkyl, optionally substituted C 2 -C 24  alkenyl, C 2 -C 24  alkynyl, and/or optionally substituted C 5 -C 24  aryl. 
     
     
         8 . The compound according to  claim 1 , wherein the optional substituent is independently an aldehyde (CHO), C 1-6  alkyl, C 1-6  alkylcarbonyl (—C(O)—C 1-6 alkyl), C 1-6  alkoxy, C 1-6  alkoxycarbonyl (—C(O)—C 1-6 alkyl), —C(O)—C 6-24  aryl), —C(O)-(5- or 6 membered heteroaryl), halo, nitrile, nitro, a fused 5- or 6 membered carbocyclic ring and/or a fused 5- or 6 membered mono- or diether ring. 
     
     
         9 . The compound according to  claim 1 , wherein (Het)Aryl is an optionally substituted phenyl. 
     
     
         10 . The compound according to  claim 9 , wherein said compound is a compound of the formula: 
       
         
           
           
               
               
           
         
         wherein X is H or OH; n is 0, 1, 2, 3, 4, or 5, and R A  is aldehyde (—CHO), C 1-6  alkyl, C 1-6  alkylcarbonyl (—C(O)—C 1-6 alkyl), C 1-6  alkoxy, C 1-6  alkoxycarbonyl (—C(O)—C 1-6 alkyl), —C(O)—C 6-24  aryl), —C(O)-(5- or 6 membered heteroaryl), halo, nitrile, or nitro; or wherein two R A 's together with the phenyl ring form a fused 5- or 6 membered carbocyclic ring or 5- or 6 membered mono- or diether ring. 
       
     
     
         11 . The compound according to  claim 10 , wherein X is H. 
     
     
         12 . The compound according to  claim 10 , wherein X is OH. 
     
     
         13 . The compound according to  claim 1 , wherein (Het)Aryl is an optionally substituted naphthyl. 
     
     
         14 . The compound according to  claim 1 , wherein (Het)Aryl is an optionally substituted 5- or 6-membered heteroaryl. 
     
     
         15 . The compound according to  claim 14 , wherein X is H. 
     
     
         16 . The compound according to  claim 14 , wherein X is OH. 
     
     
         17 . The compound according to  claim 14 , wherein p is 0. 
     
     
         18 . The compound according to  claim 14 , wherein p is 1. 
     
     
         19 . The compound according to  claim 14 , wherein at least one R B  is tert-butyl. 
     
     
         20 . The compound according to  claim 1 , wherein (Het)Aryl is an optionally substituted a furan, pyrrole, thiophene, pyrazole, imidazole, triazole, isoxazole, oxazole, thiazole, isothiazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazone, benzofuran, benzopyrrole, benzothiophene, isobenzofuran, isobenzopyrrole, isobenzothiophene, indole, isoindole, indolizine, indazole, azaindole, benzisoxazole, benzoxazole, quinoline, isoquinoline, cinnoline, quinazoline, naphthyridine, 2,3-dihydrobenzofuran, 2,3-dihydrobenzopyrrole, 2,3-dihydrobenzothiophene, dibenzofuran, xanthene, dibenzopyrol, or dibenzothiophene.