Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond-Forming Transfer Hydrogenation

被引：105

作者：

Patman, Ryan L. ^{[1
]}

Chaulagain, Mani Raj ^{[1
]}

Williams, Vanessa M. ^{[1
]}

Krische, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem & Biochem, Austin, TX 78712 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 06期

关键词：

ALLYLIC ALCOHOLS; OXIDATION LEVEL; REDUCTIVE CYCLIZATION; ASYMMETRIC-SYNTHESIS; AROMATIC-ALDEHYDES; IMINE VINYLATION; ENANTIOSELECTIVE SYNTHESIS; (+)-ALLOPUMILIOTOXIN 267A; CONJUGATED ALKYNES; CARBONYL ADDITION;

D O I：

10.1021/ja809456u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a-1l to furnish allylic alcohols 2a-21, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a-6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m-2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a.

引用

页码：2066 / +

页数：3

共 58 条

[1] Allylic amines via iridium-catalyzed C-C bond forming hydrogenation: Imine vinylation in the absence of stoichiometric byproducts or metallic reagents [J].

Barchuk, Andriy ;

Ngai, Ming-Yu ;

Krische, Michael J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (27) :8432-+

[2] Iridium-catalyzed C-C coupling via transfer hydrogenation: Carbonyl addition from the alcohol or aldehyde oxidation level employing 1,3-cyclohexadiene [J].

Bower, John F. ;

Patman, Ryan L. ;

Krische, Michael J. .

ORGANIC LETTERS, 2008, 10 (05) :1033-1035

[3] Catalytic C-C coupling via transfer hydrogenation: Reverse prenylation, crotylation, and allylation from the alcohol or aldehyde oxidation level [J].

Bower, John F. ;

Skucas, Eduardas ;

Patman, Ryan L. ;

Krische, Michael J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (49) :15134-+

[4] A general, highly enantioselective method for the synthesis of D and L α-amino acids and allylic amines [J].

Chen, YK ;

Lurain, AE ;

Walsh, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) :12225-12231

[5] TITANIUM-CATALYZED REDUCTIVE CYCLIZATION OF DELTA,EPSILON-UNSATURATED KETONES AND ALDEHYDES [J].

CROWE, WE ;

RACHITA, MJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (25) :6787-6788

[6] [2,2]paracyclophane-based N,O-ligands in alkenylzinc additions to aldehydes [J].

Dahmen, S ;

Bräse, S .

ORGANIC LETTERS, 2001, 3 (25) :4119-4122

[7] Catalyst-directed diastereoselectivity in hydrogenative couplings of acetylene to α-chiral aldehydes:: Formal synthesis of all eight L-hexoses [J].

Han, Soo Bong ;

Kong, Jong Rock ;

Krische, Michael J. .

ORGANIC LETTERS, 2008, 10 (18) :4133-4135

[8] Enantioselective reductive coupling of 1,3-enynes to glyoxalates mediated by hydrogen:: Asymmetric synthesis of β,γ-unsaturated α-hydroxy esters [J].

Hong, Young-Taek ;

Cho, Chang-Woo ;

Skucas, Eduardas ;

Krische, Michael J. .

ORGANIC LETTERS, 2007, 9 (19) :3745-3748

[9] Highly selective catalytic intermolecular reductive coupling of alkynes and aldehydes [J].

Huang, WS ;

Chan, J ;

Jamison, TF .

ORGANIC LETTERS, 2000, 2 (26) :4221-4223

[10] Hydrogen-mediated C-C bond formation:: Catalytic regio- and stereoselective reductive condensation of α-keto aldehydes and 1,3-enynes [J].

Jang, HY ;

Huddleston, RR ;

Krische, MJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (14) :4664-4668

← 1 2 3 4 5 6 →