Novel bifunctional chiral squaramide-amine catalysts for highly enantioselective addition of mono- and diketones to nitroalkenes

被引：25

作者：

Dong, Ze ^{[1
]}

Jin, Xiaoqing ^{[1
]}

Wang, Pengcheng ^{[1
]}

Min, Chang ^{[1
]}

Zhang, Jin ^{[1
]}

Chen, Zhe ^{[1
]}

Zhou, Hai-Bing ^{[1
,2
]}

Dong, Chune ^{[1
,2
]}

机构：

[1] Wuhan Univ, Coll Pharm, State Key Lab Virol, Wuhan 430071, Peoples R China

[2] Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Organofluorine Chem, Shanghai 200032, Peoples R China

来源：

ARKIVOC | 2011年

基金：

高等学校博士学科点专项科研基金;

关键词：

Chiral squaramide-amine; organocatalyst; asymmetric Michael addition; pyrrolidine; cinchonine; ASYMMETRIC MICHAEL ADDITION; SQUARIC ACID; ALPHA; ALPHA-DISUBSTITUTED ALDEHYDES; 1,3-DICARBONYL COMPOUNDS; PYRROLIDINE-THIOUREA; CONJUGATE ADDITION; KETONES; DERIVATIVES; EFFICIENT; REDUCTION;

D O I：

10.3998/ark.5550190.0012.927

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Novel bifunctional chiral squaramide-amine organocatalysts have been developed by rational combination of pyrrolidine and a cinchona alkaloid. The catalysts promoted the enantioselective Michael addition of both mono- and diketones to a broad range of nitroalkenes providing the corresponding products in moderate to high yields with excellent enantioselectivities and diastereoselectivities (up to 96% yield, 96% ee, 98: 2 dr) under mild conditions. These results demonstrate that the assembly of two chiral privileged skeletons, pyrrolidine and cinchonine with a squaramide linker is a useful strategy to reach a wider substrate scope, high reaction efficiency and enantioselectivity. The match of the chiralities between two backbones embedded in the catalysts is also critical for improving enantioselectivity.

引用

页码：367 / +

页数：61

共 65 条

[31] Efficient proline-catalyzed Michael additions of unmodified ketones to nitro olefins [J].

List, B ;

Pojarliev, P ;

Martin, HJ .

ORGANIC LETTERS, 2001, 3 (16) :2423-2425

[32] The organic approach to asymmetric catalysis [J].

List, Benjamin ;

Yang, Jung Woon .

SCIENCE, 2006, 313 (5793) :1584-1586

[33] Amide-based bifunctional organocatalysts in asymmetric reactions [J].

Liu, Xiaohua ;

Lin, Lili ;

Feng, Xiaoming .

CHEMICAL COMMUNICATIONS, 2009, (41) :6145-6158

[34] Bifunctional thiourea-promoted cascade aza-Michael-Henry-dehydration reactions: asymmetric preparation of 3-nitro-1,2-dihydroquinolines [J].

Liu, Xiaoqian ;

Lu, Yixin .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2010, 8 (18) :4063-4065

[35]

Lü SM, 2001, ACTA CHIM SINICA, V59, P587

[36] The advent and development of organocatalysis [J].

MacMillan, David W. C. .

NATURE, 2008, 455 (7211) :304-308

[37] Chiral Squaramide Derivatives are Excellent Hydrogen Bond Donor Catalysts [J].

Malerich, Jeremiah P. ;

Hagihara, Koji ;

Rawal, Viresh H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (44) :14416-+

[38] Direct asymmetric organocatalytic Michael reactions of α,α-disubstituted aldehydes with β-nitrostyrenes for the synthesis of quaternary carbon-containing products [J].

Mase, N ;

Thayumanavan, R ;

Tanaka, F ;

Barbas, CF .

ORGANIC LETTERS, 2004, 6 (15) :2527-2530

[39] Enantioselective organocatalytic conjugate addition of α-nitroacetate to α,β-unsaturated ketones in water [J].

Moon, Hyoung Wook ;

Kim, Dae Young .

TETRAHEDRON LETTERS, 2010, 51 (21) :2906-2908

[40] Evidence of anion-induced dimerization of a squaramide-based host in protic solvents [J].

Neus Pina, M. ;

Rotger, Carmen ;

Soberats, Bartomeu ;

Ballester, Pablo ;

Deya, Pere M. ;

Costa, Antoni .

CHEMICAL COMMUNICATIONS, 2007, (09) :963-965

← 1 2 3 4 5 6 7 →