Enantioselective synthesis of 1-vinyltetrahydroisoquinolines via Pd-catalyzed intramolecular asymmetric allylic amination reactions

被引：15

作者：

Chien, Chih-Wei ^{[1
]}

Shi, Ce ^{[1
]}

Lin, Chi-Feng ^{[1
]}

Ojima, Iwao ^{[1
]}

机构：

[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA

来源：

TETRAHEDRON | 2011年 / 67卷 / 35期

基金：

美国国家科学基金会;

关键词：

Tetrahydroisoquinoline; Asymmetric allylic amination; Palladium; Phosphoramidite ligand; Phosphonite ligand; COMPLEMENT MODULATORY ACTIVITY; BISBENZYLISOQUINOLINE ALKALOIDS; ISOPYRUM-THALICTROIDES; HYDROGENATION; LIGANDS; TRANSFORMATIONS; INHIBITORS;

D O I：

10.1016/j.tet.2011.05.125

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

1-Vinyltetrahydroisoquinolines serve as versatile intermediates for the synthesis of a variety of naturally occurring isoquinoline alkaloids. 1-Viny1-6,8-dimethoxytetrahydroisoquinoline 4 and 1-viny1-5,6,7-tri-methoxytetrahydroisoquinoline 6 with >90% ee by means of Pd-catalyzed intramolecular asymmetric allylic amination reactions, using MPN and BOP ligands, developed in our laboratory. The fine-tuning capability of the MPN and BOP ligands has played a significant role in the optimization of enantioselectivity. Interesting substituent effect as well as solvent effect on the product selectivity and enantioselectivity was observed. Plausible mechanisms are proposed, which can accommodate various findings, including the critical importance of the activation of the trifluoroamide moiety through its coordination to the Lewis acidic Pd(2+) metal center. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：6513 / 6523

页数：11

共 28 条

[1] A PHARMACOLOGICAL STUDY OF 2 BISBENZYLISOQUINOLINE ALKALOIDS, THALISTYLINE AND OBAMEGINE [J].

BANNING, JW ;

SALMAN, KN ;

PATIL, PN .

JOURNAL OF NATURAL PRODUCTS, 1982, 45 (02) :168-177

[2]

BENTELY KW, 1988, CHEM BIOCH ORGANIC N

[3] REACTION OF SODIUM BOROHYDRIDE WITH NICKEL ACETATE IN ETHANOL SOLUTION-A HIGHLY SELECTIVE NICKEL HYDROGENATION CATALYST [J].

BROWN, HC ;

BROWN, CA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (07) :1005-&

[4] Catalytic asymmetric transformations with fine-tunable biphenol-based monodentate ligands [J].

Chapsal, BD ;

Hua, ZH ;

Ojima, I .

TETRAHEDRON-ASYMMETRY, 2006, 17 (04) :642-657

[5] Total synthesis of enantiopure (+)-γ-lycorane using highly efficient Pd-catalyzed asymmetric allylic alkylation [J].

Chapsal, BD ;

Ojima, I .

ORGANIC LETTERS, 2006, 8 (07) :1395-1398

[6] Highly enantioselective copper-catalyzed conjugate addition of diethylzinc to nitroalkenes [J].

Choi, H ;

Hua, ZH ;

Ojima, I .

ORGANIC LETTERS, 2004, 6 (16) :2689-2691

[7] Asymmetric synthesis of isoquinoline alkaloids [J].

Chrzanowska, M ;

Rozwadowska, MD .

CHEMICAL REVIEWS, 2004, 104 (07) :3341-3370

[8] New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations [J].

Hua, ZH ;

Vassar, VC ;

Choi, H ;

Ojima, I .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (15) :5411-5416

[9] Synthesis of new chiral monodentate phosphite ligands and their use in catalytic asymmetric hydrogenation [J].

Hua, ZH ;

Vassar, VC ;

Ojima, I .

ORGANIC LETTERS, 2003, 5 (21) :3831-3834

[10] Asymmetric intramolecular allylic amination: Straightforward approach to chiral C1-substituted tetrahydroisoquinolines [J].

Ito, K ;

Akashi, S ;

Saito, B ;

Katsuki, T .

SYNLETT, 2003, (12) :1809-1812

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