Catalytic, asymmetric preparation of ketene dimers from acid chlorides

被引：60

作者：

Calter, MA ^{[1
]}

Orr, RK ^{[1
]}

Song, W ^{[1
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 24期

关键词：

D O I：

10.1021/ol0359517

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The cinchona alkaloid-catalyzed dimerization of monosubstituted ketenes generated in situ from the reaction of acid chlorides and diisopropylethylamine yields ketene dimers; in high yields and enantioselectivities. This reaction tolerates sterically demanding and functionally diverse substituents. Kinetic studies suggest that the rate-determining step for the reaction is the deprotonation of the acid chloride by the tertiary amine to form ketene and that the stereochernistry-forming step is addition of an ammonium enolate with ketene.

引用

收藏

页码：4745 / 4748

页数：4

相关论文

共 11 条

[1] First total synthesis of a natural product containing a chiral, β-diketone:: Synthesis and stereochemical reassignment of siphonarienedione and siphonarienolone [J].

Calter, MA ;

Liao, WS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (44) :13127-13129

[2] One-pot, catalytic, asymmetric syntheses of all four stereoisomers of a dipropionate synthon [J].

Calter, MA ;

Guo, X .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (16) :5308-5309

[3] Catalytic asymmetric acyl halide-aldehyde cyclocondensations. A strategy for enantioselective catalyzed cross aldol reactions [J].

Nelson, SG ;

Peelen, TJ ;

Wan, ZH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9742-9743

[4] Asymmetric synthesis using ketenes [J].

Orr, RK ;

Calter, MA .

TETRAHEDRON, 2003, 59 (20) :3545-3565

[5] ORGANISCHE KATALYSATOREN .71. ASYMMETRISCHE SYNTHESEN MIT KETENEN .4. ZUSAMMENHANGE ZWISCHEN DEM RAUMLICHEN BAU EINIGER ALKALOIDARTIGER KATALYSATOREN UND IHREN STEREOSPEZIFISCHEN WIRKUNGEN BEI ASYMMETRISCHEN ESTERSYNTHESEN [J].

PRACEJUS, H ;

MATJE, H .

JOURNAL FUR PRAKTISCHE CHEMIE, 1964, 24 (3-4) :195-205

[6] KINETICS AND MECHANISM FOR CATALYTIC ADDITION-REACTIONS ON CUMULATED DOUBLE-BOND SYSTEMS .5. BASE-CATALYZED ADDITION OF ALCOHOLS ON KETENE [J].

SAMTLEBEN, R ;

PRACEJUS, H .

JOURNAL FUR PRAKTISCHE CHEMIE-PRACTICAL APPLICATIONS AND APPLIED CHEMISTRY, 1972, 314 (01) :157-+

[7] KETENE DIMERS FROM ACID HALIDES [J].

SAUER, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1947, 69 (10) :2444-2448

[8] Catalytic, asymmetric synthesis of β-lactams [J].

Taggi, AE ;

Hafez, AM ;

Wack, H ;

Young, B ;

Drury, WJ ;

Lectka, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (32) :7831-7832

[9] The development of the first catalyzed reaction of ketenes and imines:: Catalytic, asymmetric synthesis of β-lactams [J].

Taggi, AE ;

Hafez, AM ;

Wack, H ;

Young, B ;

Ferraris, D ;

Lectka, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6626-6635

[10] Use of in situ generated ketene in the Wynberg β-lactone synthesis:: New transformations of the dichlorinated β-lactone products [J].

Tennyson, R ;

Romo, D .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (21) :7248-7252