CONJUGATE ADDITIONS OF ORGANOCUPRATES TO CYCLOALKENONE COMPLEXES OF THE CHIRAL RHENIUM LEWIS-ACID [(ETA(5)-C5H5)RE(NO)(PPH(3))](+) - ENANTIOSELECTIVE SYNTHESES OF 3-SUBSTITUTED CYCLOALKANONES

被引：31

作者：

WANG, Y ^{[1
]}

GLADYSZ, JA ^{[1
]}

机构：

[1] UNIV UTAH,DEPT CHEM,SALT LAKE CITY,UT 84112

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 04期

关键词：

D O I：

10.1021/jo00109a022

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reactions of organocuprates R(2)CuLi and cyclo alkenone complexes (+)-(R)-[(eta(5)-C5H5)Re(No)(PPh(3)) (eta(1)-0=CCH=CHCH2(CH2)(n))](+) BF4- (n = 2, 1) are conducted in THF or CH2Cl2 between -15 degrees C and -116 degrees C. Workups with aqueous HI give the corresponding S-substituted cycloalkanones and iodide complex (eta(5)-C5H5)Re(NO)(PPh(3)) (I). Under optimized conditions, 3-substituted cyclohexanones are obtained in 39-83% yields and 64-85% ee (R = Me, R; n-Bu, R; t-Bu, S; Ph, S or R), and S-substituted cyclopentanones are obtained in 50-73% yields and 79-93% ee (R = Me, R; Ph, S). Evidence for intermediate enolate complexes is presented, protocols for recycling the chiral rhenium auxiliary are described, and possible mechanisms of 1,4-asymmetric induction are discussed.

引用

页码：903 / 909

页数：7

共 57 条

[21] TRIMETHYLSILYL CHLORIDE TETRAMETHYLETHYLENEDIAMINE FACILITATED ADDITIONS OF ORGANOCOPPER REAGENTS (RCU) TO ENONES [J].