Enantioselective carbonyl-ene reaction of glyoxal derivatives catalyzed by cationic 3-oxobutylideneaminatocobalt(III) complexes

被引：26

作者：

Kezuka, S ^{[1
]}

Kogami, Y ^{[1
]}

Ikeno, T ^{[1
]}

Yamada, T ^{[1
]}

机构：

[1] Keio Univ, Fac Sci & Technol, Dept Chem, Kohoku Ku, Yokohama, Kanagawa 2238522, Japan

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 2003年 / 76卷 / 01期

关键词：

D O I：

10.1246/bcsj.76.49

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Optically active 3-oxobutylideneaminatocobalt(III) complexes were designed for the catalytic enantioselective carbonyl-ene reaction. Varieties of counter anions of cationic cobalt(IQ) complexes were screened and hexafluoroantimonate was found to be the most effective. In the presence of cobalt(IQ) hexafluoroantimonate complex 1f, the enantioselective carbonyl-ene reaction of various alkenes with glyoxal derivatives was carried out to afford the corresponding homoallylic alcohols in high yields and with high enantioselectivities. Even in the presence of 0.2 mol% cobalt(III) complexes, the reaction proceeded in high yield and with maintained high enantioselectivity. The absolute configuration of the optically active product was determined and a reasonable explanation for the enantioselection in the present carbonyl-ene reaction catalyzed by the cobalt complex was proposed.

引用

页码：49 / 58

页数：10

共 44 条

[1] The asymmetric addition of trimethylsilyl cyanide to aldehydes catalyzed by chiral (salen)titanium complexes [J].

Belokon, YN ;

Caveda-Cepas, S ;

Green, B ;

Ikonnikov, NS ;

Krustalev, VN ;

Larichev, VS ;

Moscalenko, MA ;

North, M ;

Orizu, C ;

Tararov, VI ;

Tasinazzo, M ;

Timofeeva, GI ;

Yashkina, LV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (16) :3968-3973

[2] Chiral bis(oxazoline)copper(II) complexes as Lewis acid catalysts for the enantioselective Diels-Alder reaction [J].

Evans, DA ;

Miller, SJ ;

Lectka, T ;

von Matt, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (33) :7559-7573

[3] C2-symmetric copper(II) complexes as chiral Lewis acids.: Catalytic enantioselective carbonyl-ene reactions with glyoxylate and pyruvate esters [J].

Evans, DA ;

Tregay, SW ;

Burgey, CS ;

Paras, NA ;

Vojkovsky, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (33) :7936-7943

[4] Bis(oxazoline) and bis(oxazolinyl)pyridine copper complexes as enantioselective Diels-Alder catalysts: Reaction scope and synthetic applications [J].

Evans, DA ;

Barnes, DM ;

Johnson, JS ;

Lectka, R ;

von Matt, P ;

Miller, SJ ;

Murry, JA ;

Norcross, RD ;

Shaughnessy, EA ;

Campos, KR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (33) :7582-7594

[5] C2-symmetric copper(II) complexes as chiral Lewis acids.: Enantioselective catalysis of the glyoxylate-ene reaction [J].

Evans, DA ;

Burgey, CS ;

Paras, NA ;

Vojkovsky, T ;

Tregay, SW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (23) :5824-5825

[6] THERMODYNAMIC BEHAVIOR OF ALKANES IN SUPERACID MEDIA [J].

FABRE, PL ;

DEVYNCK, J ;

TREMILLON, B .

CHEMICAL REVIEWS, 1982, 82 (06) :591-614

[7]

GRONDIN J, 1976, B SOC CHIM FR I-PHYS, P1779

[8] Chiral palladium(II)-catalyzed asymmetric glyoxylate-ene reaction:: Alternative approach to the enantioselective synthesis of α-hydroxy esters [J].

Hao, J ;

Hatano, M ;

Mikami, K .

ORGANIC LETTERS, 2000, 2 (25) :4059-4062

[9] Design and development of highly effective lewis acid catalysts for enantioselective Diels-Alder reactions [J].

Huang, Y ;

Iwama, T ;

Rawal, VH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (21) :5950-5951

[10] Highly enantioselective cyclopropanation of styrenes and diazoacetates catalyzed by 3-oxobutylideneaminatocobalt(II) complexes, Part 1. Designs of cobalt complex catalysts and the effects of donating ligands [J].

Ikeno, T ;

Sato, M ;

Sekino, H ;

Nishizuka, A ;

Yamada, T .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2001, 74 (11) :2139-2150

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