Base-catalyzed silylation of terminal olefinic c-h bonds

Patent metadata

Field	Value
Publication number	US-2016347776-A1
Application number	US-201615166405-A
Country	US
Kind code	A1
Filing date	May 27, 2016
Priority date	May 29, 2015
Publication date	Dec 1, 2016
Grant date	—

Abstract

The present invention is directed to a mild, efficient, and general direct C(sp 2 )-H bond silylation of terminal olefins. Various embodiments includes methods, each method comprising or consisting essentially of contacting at least one organic substrate comprising a terminal olefinic C—H bond, with a mixture of at least one organosilane, organosilane, or mixture thereof and an alkali metal alkoxide or alkali metal hydroxide, such that the contacting results in the formation of a silylated olefinic product. The systems associated with these methods are also disclosed.

First claim

What is claimed:

1 . A method comprising contacting at least one organic substrate comprising a terminal olefin with:
(a) an organosilane, organodisilane, or mixture thereof; and (b) an alkali metal alkoxide, an alkali metal hydroxide, an alkaline earth metal alkoxide, and alkaline earth hydroxide, an alkali metal amide, or a mixture thereof, such that the contacting results in the formation of a terminally silylated olefinic product.

2 . The method of claim 1 , wherein the organosilane has a structure of Formula (I) and the organodisilane has a structure of Formula (II):
(R) 3-m Si(H) m+1   (I)
(R) 3-m (H) m Si—Si(R) 3-m (H) m   (II)
where: m is independently 0, 1, or 2; and each R is independently optionally substituted C 1-24 alkyl or heteroalkyl, optionally substituted C 2-24 alkenyl or heteroalkenyl, optionally substituted C 2-24 alkynyl or heteroalkynyl, optionally substituted 6 to 18 ring membered aryl or 5 to 18 ring membered heteroaryl, optionally substituted 6 to 18 ring-membered alkaryl or 5 to 18 ring-membered heteroalkaryl, optionally substituted 6 to 18 ring-membered aralkyl or 5 to 18 ring-membered heteroaralkyl, optionally substituted —O—C 1-24 alkyl or heteroalkyl, optionally substituted 6 to 18 ring-membered aryloxy or 5 to 18 ring-membered heteroaryloxy, optionally substituted 6 to 18 ring-membered alkaryloxy or 5 to 18 ring-membered heteroalkaryloxy, or optionally substituted 6 to 18 ring-membered aralkoxy or 5 to 18 ring-membered heteroaralkoxy, 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, 5 to 12 ring-membered 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.

3 . The method of claim 1 , wherein the organosilane or organodisilane is an organosilane.

4 . The method of claim 1 , wherein the organosilane or organodisilane is an organodisilane.

5 . The method of claim 1 , wherein the organosilane comprises (R) 3 SiH, (R) 2 SiH 2 , or (R)SiH 3 , where R is independently at each occurrence optionally substituted C 1-18 alkoxy, optionally substituted C 1-18 alkyl, optionally substituted C 2-18 alkenyl, optionally substituted 6-18 ring membered aryl, 6-18 ring membered aryloxy, 5-18 ring membered heteroaryl, 6-18 ring membered aralkyl, 6-18 ring membered aralkyloxy, or 6-10 ring membered heteroaralkyl.

6 . The method of claim 1 , wherein the organodisilane comprises (R) 3-m (H) m Si—Si(R) 3-m (H) m or (R) 3 Si—Si(R) 3 , where R is independently at each occurrence optionally substituted C 1-18 alkoxy, optionally substituted C 1-18 alkyl, optionally substituted C 2-18 alkenyl, optionally substituted C 6-18 aryl, optionally substituted C 6-18 aryloxy, optionally substituted 5-18 ring membered heteroaryl, optionally substituted 6-18 ring membered aralkyl, optionally substituted 6-18 ring membered aralkyloxy, or optionally substituted 6-18 ring membered heteroaralkyl.

7 . The method of claim 1 , wherein R is independently at each occurrence methyl, ethyl, propyl, butyl, propyl, phenyl, biphenyl, phenoxy, benzyl, benzyloxy, or pyridinyl.

8 . The method of claim 1 , wherein the alkali metal hydroxide comprises sodium hydroxide (NaOH), potassium hydroxide (KOH), or a mixture thereof.

9 . The method of claim 1 , wherein the alkali metal alkoxide comprises a sodium alkoxide, potassium alkoxide, or mixture thereof.

10 . The method of claim 1 , wherein the alkoxide comprises a linear, branched, or cyclic saturated hydrocarbon group containing 1 to 12 carbon atoms.

11 . The method of claim 1 , wherein the alkoxide comprises sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium isopropoxide, sodium n-butoxide, sodium sec-butoxide, sodium tert-butoxide, sodium n-pentoxide, sodium 2-pentoxide, sodium 3-pentoxide, sodium iso-pentoxide, potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium isopropoxide, potassium n-butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium n-pentoxide, potassium 2-pentoxide, potassium 3-pentoxide, or potassium iso-pentoxide.

12 . The method of claim 1 , wherein the least one organic substrate comprising the terminal olefin has a formula:

where p is 0 or 1; R 1 and R 2 independently comprises H, an optionally substituted C 1-18 alkyl, optionally substituted C 2-18 alkenyl, C 2-18 optionally substituted alkynyl, optionally substituted C 6-18 aryl, optionally substituted C 1-18 heteroalkyl, optionally substituted 5-6 ring membered heteroaryl, optionally substituted 5-6 ring membered aralkyl, optionally substituted 5-6 ring membered heteroaralkyl, or optionally substituted metallocene, provided that R 1 and R 2 are not both H.

13 . The method of claim 12 , wherein each R 1 and R 2 independently comprises:
(a) an optionally substituted C 1-18 linear alkyl, an optionally substituted branched C 1-18 alkyl, or an optionally substituted C 3-18 cycloalkyl; (b) an optionally substituted linear C 2-18 alkenyl, an optionally substituted branched C 2-18 alkenyl, or an optionally substituted C 3-18 cycloalkenyl; (c) an optionally substituted linear C 1-18 heteroalkyl, an optionally substituted branched C 1-18 heteroalkyl, or an optionally substituted C 1-18 heterocycloalkyl; (d) an optionally substituted 6-18 ring membered aryl, an optionally substituted 6-18 ring membered aralkyl, an optionally substituted 6-18 ring membered aryloxy, an optionally substituted 6-18 ring membered aralkyloxy, optionally substituted 5-18 ring membered heteroaryl, or an optionally substituted optionally substituted 5-18 ring membered heteroaralkyl, optionally substituted 5-18 ring membered heteroaryloxy, or an optionally substituted optionally substituted 5-18 ring membered heteroaralkyloxy; or (e) hydrogen, provided that R 1 and R 2 are not both hydrogen when p=0.

14 . The method of claim 12 , wherein the terminally silylated olefinic product has a formula:

15 . The method of claim 12 , wherein when p=1, the terminally silylated olefinic product has a formula:

16 . The method of claim 12 , further comprising polymerizing the terminally silylated olefinic product

17 . The method of claim 1 , wherein the method consists essentially of contacting at least one organic substrate comprising a terminal olefin with a mixture of an organosilane or organodisilane and an alkali metal alkoxide and/or an alkali metal hydroxide, such that the contacting results in the formation of a terminally silylated olefinic product.

18 . The method of claim 1 , wherein the method is conducted in the absence of added transition

Assignees

• California Inst Of Techn

Inventors

• Toutov Anton
• Liu Wenbo
• Betz Kerry
• Fedorov Alexey
• Stoltz Brian M
• Grubbs Robert H

Classifications

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title

• C08F30/08

  containing silicon · CPC title

• C07F17/02

  of metals of Groups 8, 9 or 10 of the Periodic Table · CPC title