Base-catalyzed silylation of terminal olefinic C—H bonds

Patent metadata

Field	Value
Publication number	US-10059726-B2
Application number	US-201615166405-A
Country	US
Kind code	B2
Filing date	May 27, 2016
Priority date	May 29, 2015
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

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, an alkaline earth metal 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 optionally substituted C 1-24 heteroalkyl, optionally substituted C 2-24 alkenyl or optionally substituted C 2-24 heteroalkenyl, optionally substituted C 2-24 alkynyl or optionally substituted C 2-24 heteroalkynyl, optionally substituted 6 to 18 ring membered aryl or optionally substituted 5 to 18 ring membered heteroaryl, optionally substituted 6 to 18 ring-membered alkaryl or optionally substituted 5 to 18 ring-membered heteroalkaryl, optionally substituted 6 to 18 ring-membered aralkyl or optionally substituted 5 to 18 ring-membered heteroaralkyl, optionally substituted —O—C 1-24 alkyl or optionally substituted —O—C 1-24 heteroalkyl, optionally substituted 6 to 18 ring-membered aryloxy or optionally substituted 5 to 18 ring-membered heteroaryloxy, optionally substituted 6 to 18 ring-membered alkaryloxy or optionally substituted 5 to 18 ring-membered heteroalkaryloxy, or optionally substituted 6 to 18 ring-membered aralkoxy or optionally substituted 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 optionally provide a tether to an insoluble or sparingly soluble support media comprising alumina, silica, or carbon.

3. The method of claim 2 , where m is 1 or 2, further comprising reacting the terminally silylated olefinic product with an aromatic substrate under conditions sufficient to silylate the aromatic substrate with the terminally silylated olefinic product to form a product of the silylation of the aromatic substrate with the terminally silylated olefinic product.

4. The method of claim 3 , wherein the 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, 0 to 3, 0 to 2, or 0 to 1;
R′ is a functional group “Fn,” or (R′) p is an optionally substituted fused alicyclic, heteroalicyclic, aryl or heteroaryl moiety, wherein “Fn” is C 1-24 alkyl, C 2-24 alkenyl, C 2-24 alkynyl, C 6-24 awl, C 7-24 alkaryl, C 6-24 aralkyl, halo, C 1-24 alkoxy, C 2-24 alkenyloxy, C 2-24 alkynyloxy, C 6-24 aryloxy, C 6-24 aralkyloxy, C 6-24 alkaryloxy, C 1-24 alkylcarbonyl, C 6-24 arylcarbonyl, C 2-24 alkylcarbonyloxy, C 6-24 arylcarbonyloxy, C 2-24 alkoxycarbonyl ((CO)—O-alkyl), C 6-24 aryloxycarbonyl, halocarbonyl C 2-24 alkylcarbonato, C 6-24 arylcarbonato, carboxy (—COOH), carboxylato (—COO—), carbamoyl, mono-(C 1-24 alkyl substituted carbamoyl, di-(C 1-24 alkyl)-substituted carbamoyl, mono-(C 5-24 aryl)-substituted carbamoyl, di-(C 5-24 aryl)substituted carbamoyl, thiocarbamoyl (—(CS)NH 2 ), mono-(C 1-24 alkyl)-substituted thiocarbamoyl, di-(C 1-24 substituted thiocarbamoyl, mono-(C 6-24 aryl)substituted thiocarbamoyl, di-(C 6-24 aryl)-substituted thiocarbamoyl, carbamido, cyano, cyanato, thiocyanato, formyl, thioformyl, amino, mono-(C 1-24 alkyl)-substituted amino, di-(C 1-24 alkyl)-substituted amino, mono-(C 6-24 aryl)substituted amino, di-(C 6-24 aryl)-substituted amino, C 1-24 alkylamido, C 6-24 arylamido, imino, alkylimino, arylimino, nitro, nitroso, sulfonate, C 1-24 alkylsulfanyl (—S-alkyl), C 6-24 arylsulfanyl (—S-aryl), C 1-24 alkylsulfinyl (—(SO)-alkyl), C 6-24 arylsulfinyl (—(SO)-aryl), C 1-24 alkylsulfonyl, mono-C 1-24 alkylaminosulfonyl, di-C 1-24 alkylaminosulfonyl, C 6-24 aryl sulfonyl, or boronato; and
R″ is an amine protecting group or an optionally substituted alkyl, aryl, heteroaryl, alkaryl or alk-heteroaryl;
and wherein the terminally silylated olefinic product is introduced to the aromatic substrate on a 5 or 6-membered ring of the aromatic substrate.

5. The method of claim 2 , where m is 1 or 2, further comprising reacting the terminally silylated olefinic product with an organic substrate comprising a terminal alkyne, to form a silylated terminal alkynyl moiety.

6. The method of claim 5 , wherein the organic substrate comprising the terminal alkynyl C—H bond has a formula:
R 3 —C≡C—H,

where R 3 comprises an optionally substituted C 1-18 alkyl, optionally substituted C 2-18 alkenyl, optionally substituted C 2-18 alkynyl, optionally substituted C 1-18 membered heteroalkyl, optionally substituted 6-18 ring membered aryl, optionally substituted 6-18 ring membered aryloxy, optionally substituted 6-18 ring membered aralkyl, optionally substituted 6-18 ring membered aralkyloxy, optionally substituted 5-18 ring membered heteroaryl, optionally substituted 5-18 ring membered heteroaryloxy, optionally substituted 5-18 ring membered heteroarylalkyl, optionally substituted 5-18 ring membered heteroaralkyloxy, or optionally substituted metallocene.

7. The method of claim 2 , where m is 0, 1, or 2 further comprising reacting the terminally silylated olefinic product with:
(a) water, alcohol, hydrogen cyanide, hydrogen chloride, dihalogen, or carboxylic acid under conditions known to give corresponding hydroxy, alkoxy, cyano, halo, or ester products;
(b) an alkyl halide, an aryl halide, or a heteroaryl halide, in the presence of a palladium catalyst, under cross-coupling conditions sufficient to replace the silyl group by the corresponding alkyl, aryl, or heteroaryl moiety;
(c) alkyl lithium or potassium tert-butoxide, then with an alkyl halide to form an alkyl substituted vinyl silyl product;
(d) IC1 or I 2 so as to form a terminal vinyl iodide with the displacement of the silyl group;
(e) a polyolefin so as to form a silane grafted polyolefin;
(f) an organic peroxide to form a terminal silylated peroxide, which when treated with a strong acid forms an aldehyde moiety;
(g) a fluoride source, hydrogen peroxide, and base to form an aldehyde or ketone, according to the well-known Tamao-Fleming Oxidation reaction;
(h) an iodosyl benzene to form a vinyliodonium tetrafluoroborate; or
(i) an acid chloride, aldehyde, epoxide, imine, ketal, or ketone, with a Lewis acid, for example TiCl 4 or BF 3 *OEt 2 , under conditions generally recognized as associated with the Hosomi-Sakurai Allylation reaction to form the corresponding allyl derivative.

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

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

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