Catalytic asymmetric addition of diorganozinc reagents to N-phosphinoylalkylimines

被引：88

作者：

Cóté, A ^{[1
]}

Boezio, AA ^{[1
]}

Charette, AB ^{[1
]}

机构：

[1] Univ Montreal, Dept Chem, Montreal, PQ H3C 3J7, Canada

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2004年 / 101卷 / 15期

关键词：

D O I：

10.1073/pnas.0307096101

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The synthesis of alpha-chiral amines bearing two alkyl groups has been hampered by the accessibility and stability of the alkylimine precursor. Herein, we report an efficient strategy to generate the alkyl-substituted imine in situ that is compatible with the Me-DuPHOS monoxide-Cu(I) catalyzed addition of diorganozinc reagents. The sulfinic acid adduct of the imine is readily prepared by mixing diphenylphosphinic amide, the aldehyde, and sulfinic acid. The sulfinic acid adduct is generally isolated by filtration. The addition of diorganozinc reagents in the presence of Me-DuPHOS monoxide-Cu(I) and the in situ-generated imines affords the corresponding alpha-chiral amines in high yields and enantiomeric excesses.

引用

页码：5405 / 5410

页数：6

共 34 条

[1] Additions of organometallic reagents to C=N bonds: Reactivity and selectivity [J].

Bloch, R .

CHEMICAL REVIEWS, 1998, 98 (04) :1407-1438

[2] Asymmetric, catalytic synthesis of α-chiral amines using a novel bis(phosphine) monoxide chiral ligand [J].

Boezio, AA ;

Pytkowicz, J ;

Côté, A ;

Charette, AB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (47) :14260-14261

[3] Catalytic enantioselective addition of dialkylzinc to N-diphenylphosphinoylimines.: A practical synthesis of α-chiral amines [J].

Boezio, AA ;

Charette, AB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (07) :1692-1693

[4] The asymmetric dialkylzinc addition to imines catalyzed by [2.2]paracyclophane-based N,O-ligands [J].

Dahmen, S ;

Bräse, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (21) :5940-5941

[5] ORGANOCERIUM ADDITIONS TO SAMP-HYDRAZONES - GENERAL-SYNTHESIS OF CHIRAL AMINES [J].

DENMARK, SE ;

WEBER, T ;

PIOTROWSKI, DW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (07) :2224-2225

[6] N-tert-Butanesulfinyl imines:: Versatile intermediates for the asymmetric synthesis of amines [J].

Ellman, JA ;

Owens, TD ;

Tang, TP .

ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (11) :984-995

[7] ENANTIOSELECTIVE SYNTHESIS OF ALPHA-SUBSTITUTED PRIMARY AMINES BY NUCLEOPHILIC-ADDITION TO ALDEHYDE-SAMP HYDRAZONES [J].

ENDERS, D ;

SCHUBERT, H ;

NUBLING, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (12) :1109-1110

[8] Asymmetric synthesis of amines by nucleophilic 1,2-addition of organometallic reagents to the CN-double bond [J].

Enders, D ;

Reinhold, U .

TETRAHEDRON-ASYMMETRY, 1997, 8 (12) :1895-1946

[9] Copper-amidophosphine catalyst in asymmetric addition of organozinc to imines [J].

Fujihara, H ;

Nagai, K ;

Tomioka, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (48) :12055-12056

[10] Rhodium-catalyzed asymmetric arylation of imines with organostannanes. Asymmetric synthesis of diarylmethylamines [J].

Hayashi, T ;

Ishigedani, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (05) :976-977

← 1 2 3 4 →