Silylations of aromatic substrates with base-activated organosilanes

Patent metadata

Field	Value
Publication number	US-11230520-B2
Application number	US-202117142751-A
Country	US
Kind code	B2
Filing date	Jan 6, 2021
Priority date	Oct 2, 2012
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

The present disclosure describes methods for silylating aromatic organic substrates, and associated chemical systems, said methods comprising or consisting essentially of contacting the aromatic 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.

First claim

The invention claimed is:

1. A method of preparing silylated compound comprising a moiety of Formula (I) or Formula (II):

the method comprising:
contacting a substrate containing a

moiety with (a) a hydrosilane of formula (R 1 ) 3-m Si(H) m+1 and (b) at least one strong base comprising an alkali metal alkoxide, an alkali metal hydride, an alkaline earth metal hydride, or potassium bis(trimethylsilyl)amide, under conditions to form the silylated compound, the method resulting in the formation of the silylated compound comprising the moiety of Formula (I) or Formula (II);
wherein
m is 0, 1, or 2;
R 1 is independently optionally substituted C 1-12 alkyl, C 1-12 heteroalkyl, or an optionally substituted 5- or 6-membered aryl or heteroaryl, and, if substituted, the substituents are independently alkyl, alkenyl, aryl, heteroaryl, hydroxyl, C 1 -C 20 alkoxy, C 5 -C 20 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 20 aryloxycarbonyl, amino, optionally protected carboxyl, carboxylato, cyano, halo, 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, amido, imino, nitro, nitroso, mercapto, optionally protected formyl, C 1 -C 20 thioester, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, or boryl;
X is NR 2 , O, or S;
R 2 is an amine protecting group, an optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkaryl or optionally substituted alk-heteroaryl;

is a heteroaromatic moiety containing y additional nitrogens in the ring structure, where y=0 or 1 when X is O or S, or y=0, 1, or 2 when X is NR 2 ; and

is an aromatic moiety containing x nitrogen atoms in the ring structure, wherein x is 0, 1, or 2.

2. The method of claim 1 , wherein the moiety of formula (I) or (III) is a furan, pyrrole, thiophene, pyrazole, imidazole, triazole, isoxazole, oxazole, thiazole, isothiazole, or oxadiazole.

3. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

4. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

5. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (I) having a structure of:

6. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

7. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

8. The method of claim 1 , resulting in the formation of the silylated compound comprising the moiety of Formula (II) having a structure of:

9. The method of claim 1 , wherein the at least one strong base comprises the alkali metal alkoxide.

10. The method of claim 9 , wherein the alkali metal alkoxide comprises a potassium alkoxide or a cesium alkoxide.

11. The method of claim 10 , wherein the potassium alkoxide or cesium alkoxide comprises a C 1-12 linear or branched alkyl moiety or a C 5-10 aryl or heteroaryl moiety.

12. The method of claim 9 , wherein the alkali metal alkoxide comprises potassium methoxide, potassium ethoxide, a potassium propoxide or a potassium butoxide.

13. The method of claim 9 , wherein the alkali metal alkoxide comprises potassium tert-butoxide.

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

15. The method of claim 1 , wherein:
(a) the hydrosilane and the at least one strong base are present together at a molar ratio, with respect to one another, in a range of from 20:1 to 1:1; and/or
(b) the at least one strong base and organic substrate are present together at a molar ratio, with respect to one another, in a range of from 0.01:1 to 0.9:1.

16. The method of claim 1 , wherein m=0.

17. The method of claim 1 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

18. The method of claim 3 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

19. The method of claim 6 , wherein m=1, optionally wherein R 1 is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

20. The method of claim 1 , wherein m=2.

21. The method of claim 1 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

22. The method of claim 3 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

23. The method of claim 6 , wherein R 1 is independently optionally substituted C 1-12 alkyl, optionally substituted heteroaryl or optionally substituted C 2-12 heterocycloalkyl.

24. The method of claim 1 where R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

25. The method of claim 3 , wherein R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

26. The method of claim 6 , wherein R 1 is independently optionally substituted cyclic alkyl or branched alkyl or cyclic or branched heteroalkyl.

27. The method of claim 1 , wherein R 1 is independently tert-alkyl.

28. The method of claim 3 , wherein R 1 is independently tert-alkyl.

29. The method of claim 6 , wherein R 1 is independently tert-alkyl.

30. The method of claim 17 , wherein R is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

31. The method of claim 18 , wherein R is independently tert-butyl, —C(CH 3 ) 2 (CN), pyridine, or an alkyl substituted heterocycloalkyl.

32. The method of claim 19 , wherein R is independently tert-butyl, —C(CH 3 ) 2 (CN), py

Assignees

• California Inst Of Techn

Inventors

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

Classifications

• C07F7/0814

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

• C07C1/22 Primary

  by reduction · CPC title

• C07F7/0896

  Compounds with a Si-H linkage · CPC title

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title

• C07C319/06

  from sulfides, hydropolysulfides or polysulfides · CPC title