Racemic but Tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes:: Highly enantioselective ene-type cyclization of 1,6-enynes

被引：63

作者：

Mikami, K ^{[1
]}

Kataoka, S ^{[1
]}

Yusa, Y ^{[1
]}

Aikawa, K ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Appl Chem, Tokyo 1528552, Japan

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 21期

关键词：

D O I：

10.1021/ol048604l

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degreesC, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.

引用

页码：3699 / 3701

页数：3

共 27 条

[11]

2-3

[12]

Mendez M., 2003, Chem, V16, P397

[13] Highly enantioselective spiro cyclization of 1,6-enynes catalyzed by cationic skewphos rhodium(I) complex [J].

Mikami, K ;

Yusa, Y ;

Hatano, M ;

Wakabayashi, K ;

Aikawa, K .

CHEMICAL COMMUNICATIONS, 2004, (01) :98-99

[14] Palladium-catalyzed carbocyclization of 1,6-enynes leading to six-membered rings or oxidized five-membered trifluoroacetates [J].

Mikami, K ;

Hatano, M .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (16) :5767-5769

[15] Tropos or atropos? That is the question! [J].

Mikami, K ;

Aikawa, K ;

Yusa, Y ;

Jodry, JJ ;

Yamanaka, M .

SYNLETT, 2002, (10) :1561-1578

[16] Asymmetric activation of the Pd catalyst bearing the Tropos biphenylphosphine (BIPHEP) ligand with the chiral diaminobinaphthyl (DABN) activator [J].

Mikami, K ;

Aikawa, K ;

Yusa, Y .

ORGANIC LETTERS, 2002, 4 (01) :95-97

[17] Resolution of Pd catalyst with tropos biphenylphosphine (BIPHEP) ligand by DM-DABN:: Asymmetric catalysis by an enantiopure BIPHEP-Pd complex [J].

Mikami, K ;

Aikawa, K ;

Yusa, Y ;

Hatano, M .

ORGANIC LETTERS, 2002, 4 (01) :91-94

[18]

Mikami K, 1999, ANGEW CHEM INT EDIT, V38, P495, DOI 10.1002/(SICI)1521-3773(19990215)38:4<495::AID-ANIE495>3.0.CO

[19]

2-O

[20] 2,2'-BIS(DIPHENYLPHOSPHINO)-1,1'-BINAPHTHYL (BINAP) - A NEW ATROPISOMERIC BIS(TRIARYL)PHOSPHINE - SYNTHESIS AND ITS USE IN THE RH(I)-CATALYZED ASYMMETRIC HYDROGENATION OF ALPHA-(ACYLAMINO)ACRYLIC ACIDS [J].

MIYASHITA, A ;

TAKAYA, H ;

SOUCHI, T ;

NOYORI, R .

TETRAHEDRON, 1984, 40 (08) :1245-1253

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