Transition-metal-free silylation of aromatic compounds

Patent metadata

Field	Value
Publication number	US-9309269-B2
Application number	US-201514628641-A
Country	US
Kind code	B2
Filing date	Feb 23, 2015
Priority date	Oct 2, 2012
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

The present invention describes chemical systems and methods for silylating aromatic organic substrates, said system comprising a mixture of (a) at least one organosilane and (b) at least one strong base, said system being substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to silylate the aromatic substrate; wherein said system is substantially free of a transition-metal compound.

First claim

What is claimed:

1. A chemical system for silylating aromatic substrates comprising an aromatic moiety, said system comprising a mixture of (a) at least one organosilane and (b) at least one strong hydride or alkoxide base, said system being capable of silylating the organic substrate; wherein the system is substantially free of transition-metal compounds.

2. The system of claim 1 , wherein the mixture further comprises an optionally substituted tetraalkylethylenediamine (e.g., tetramethylethylenediamine), an optionally substituted 1,10-phenanthroline derivative, an optionally substituted 2,2′-bipyridine derivatives, or an optionally substituted 4-dimethylaminopyridine derivative.

3. The system of claim 1 , that is substantially free of water, oxygen, or both water and oxygen.

4. The system of claim 1 , wherein at least one organosilane comprises an organosilane of Formula (I) or Formula (II):
(R) 4-m Si(H) m   (I)

R—[—SiH(R)—O—] n R  (II)

where
m is 1, 2, or 3;
n is 10 to 100; and
each R is independently optionally substituted C 1-12 alkyl or heteroalkyl, optionally substituted C 5-20 aryl or heteroaryl, optionally substituted C 6-30 alkaryl or heteroalkaryl, optionally substituted C 6-30 aralkyl or heteroaralkyl, optionally substituted —O—C 1-12 alkyl or heteroalkyl, optionally substituted —O—C 5-20 aryl or heteroaryl, optionally substituted —O—C 6-30 alkaryl or heteroalkaryl, or optionally substituted —O—C 6-30 aralkyl or heteroaralkyl, and, if substituted, the substituents may be phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C 1 -C 20 alkylsulfanyl, C 5 -C 20 arylsulfanyl, C 1 -C 20 alkylsulfonyl, C 5 -C 20 arylsulfonyl, C 1 -C 20 alkylsulfinyl, C 5 -C 20 arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C 1 -C 20 alkoxy, C 5 -C 20 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 20 aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C 1 -C 20 thioester, cyano, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group, where the metalloid is Sn or Ge, where the substituents may optionally provide a tether to an insoluble or sparingly soluble support media comprising alumina, silica, or carbon.

5. The system of claim 1 , wherein the organosilane is (R) 3 SiH or (R) 2 SiH 2 , where each R is independently C 1-6 alkyl.

6. The system of claim 1 , wherein the at least one strong base comprises an alkali or alkaline earth metal hydride or alkoxide.

7. The system of claim 1 , wherein the at least one strong base comprises an alkali or alkaline earth metal hydride.

8. The system of claim 7 , wherein the at least one strong base comprises calcium hydride or potassium hydride.

9. The system of claim 1 , wherein the at least one strong base comprises an alkali or alkaline earth metal alkoxide.

10. The system of claim 9 , wherein the at least one alkoxide comprises a C 1-12 linear or branched alkyl moiety or a C 5-10 aryl or heteroaryl moiety.

11. The system of claim 10 , wherein the at least one alkoxide comprises methoxide, ethoxide, propoxide, butoxide, or 2-ethyl-hexyl alkoxide.

12. The system of claim 6 , wherein the alkali or alkaline earth metal hydride or alkoxide is a potassium or cesium alkoxide.

13. The system of claim 1 , where the organosilane is triethylsilane and the strong base is potassium tert-butoxide.

14. The system of claim 1 , wherein the organosilane and the at least one strong base are present together at a molar ratio, with respect to one another, in a range of from about 20:1 to about 1:1.

15. The system of claim 1 , wherein the at least one strong base and substrate are present together at a molar ratio, with respect to one another, in a range of from about 0.01:1 to about 0.9:1.

16. The system of claim 1 , wherein the organic substrate comprises an optionally substituted benzene, biphenyl, naphthalene, or anthracene ring structure.

17. The system of claim 1 , wherein the organic substrate comprises an exocyclic aromatic C—X bond, where X is N, O, or S.

18. The system of claim 17 , wherein the organic substrate comprises an exocyclic aromatic C—X bond and the silylation occurs ortho to the exocyclic C—X bond.

19. The system of claim 1 , wherein the organic substrate comprises a heteroaryl moiety.

20. The system of claim 19 , wherein the substrate comprises an optionally substituted furan, pyrrole, thiophene, pyrazole, imidazole, benzofuran, benzopyrrole, benzothiophene, indole, azaindole, dibenzofuran, xanthene, dibenzopyrrole, or a dibenzothiophene.

21. The system of claim 1 , wherein the organic aromatic substrate comprises at least one of the following moieties:

where
X is N—R″, O, or S;
Y is H, N(R″) 2 , O—R″, or S—R″
p is 0 to 4;
R′ is a halo, hydroxyl, sulfhydryl, alkoxy, aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy), alkoxycarbonyl, aryloxycarbonyl, halocarbonyl, alkylcarbonato, arylcarbonato, carboxylato (—COO—), dialkyl-substituted carbamoyl, di haloalkyl-substituted carbamoyl, di aryl-substituted carbamoyl, di-alkyl-substituted thiocarbamoyl, di-aryl-substituted thiocarbamoyl, di-N-alkyl), N-aryl-substituted thiocarbamoyl, cyano, cyanato, thiocyanato, di-alkyl-substituted amino, di-aryl-substituted amino, arylimino (—CR═N(aryl), where R=alkyl, aryl, alkaryl, aralkyl), nitro, nitroso, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, boronato (—B(OR) 2 where R is alkyl or other hydrocarbyl); or (R′) p is an optionally substituted fused alicyclic, heteroalicyclic, aryl or heteroaryl moiety; and
R″ is an amine protecting group or an optionally substituted alkyl, aryl, heteroaryl, alkaryl or alk-heteroaryl, preferably optionally substituted C 1 -C 6 alkyl, phenyl, tolyl, benzyl, or phenethyl.

22. The system of claim 1 , wherein the substrate comprises at least one of the following moieties:

where
X is N—R″, O, or S;
Y is H, N(R″) 2 , O—R″, or S—R″
p is 0 to 4;
R′ is a halo, hydroxyl, sulfhydryl, alkoxy, aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy), alkoxycarbonyl, aryloxycarbonyl, halocarbonyl, alkylcarbonato, arylcarbonato, carboxylato (—COO—), dialkyl-substituted carbamoyl, di haloalkyl-substituted carbamoyl, di aryl-substituted carbamoyl, di-alkyl-substituted thiocarbamoyl, di-aryl-substituted thiocarbamoyl, di-N-alkyl), N-aryl-substituted thiocarbamoyl, cyano, cyanato, thiocyanato, di-alkyl-substituted amino, di-aryl-substituted amino, arylimino (—CR═N(aryl), where R=alkyl, aryl, alkaryl, aralkyl), nitro, nitroso, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, boronato (—B(OR) 2 where R is alkyl or other hydrocarbyl); or (R′) p is an optionally substituted fused alicyclic, heteroalicyclic, aryl or heteroaryl moiety; and
R″ is an amine protecting group or an optionally substituted alkyl, aryl, heteroaryl, alkaryl or alk-heteroaryl, preferably optionally substituted C 1 -C 6 alkyl, phenyl, tolyl, benzyl, or phenethyl.

23. The system of claim 21 , wherein the organic substrate comprises a heteroaryl moiety of structure:

and th

Assignees

• California Inst Of Techn

Inventors

• Grubbs Robert H
• Fedorov Alexey
• Toutov Anton
• Betz Kerry

Classifications

• C07F7/0812

  comprising a heterocyclic ring · CPC title

• C07F7/0814

  said ring is substituted at a C ring atom by Si · CPC title

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title

• C07F7/0896

  Compounds with a Si-H linkage · CPC title

• C07F7/0818

  Chemistry & Metallurgy · mapped topic