SOLVENT-CONTROLLED STEREOSELECTIVITY IN THE HYDROSILYLATION OF ALK-1-YNES CATALYZED BY RHODIUM COMPLEXES

被引：53
作者：
TAKEUCHI, R
TANOUCHI, N
机构：
[1] Department of Chemistry, Yokohama City University, Kanazawa-ku
来源：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1994年 / 20期
关键词：
D O I：
10.1039/p19940002909
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
New methodology for complete control of stereoselectivity in:the hydrosilylation of alk-1-ynes is described. Alk-1-ynes react with triethylsilane to produce both (E)- and (Z)-vinylsilane, depending upon the reaction conditions, with high selectivity (91-97%). A [{Rh(cod)Cl}(2)]-catalysed reaction using ethanol as a solvent gave rise to Z-selective conditions whilst E-selective conditions were achieved in [{Rh(cod)Cl}(2)]/PPh(3) or [RhCl(PPh(3))(3)]-catalysed reactions using acetonitrile as a solvent. A cationic rhodium(I) phosphine complex generated in situ was found to be the active species in E-selective conditions.
引用
收藏
页码：2909 / 2913
页数：5
相关论文
共 33 条
[1]  
AHMAD N, 1974, INORG SYNTH, V15, P58
[2]  
AHMAD N, 1974, INORG SYNTH, V15, P59
[3]  
BENNETT MA, 1961, J CHEM SOC, P1418
[4]   HYDROSILYLATION OF 1-PENTYNE BY TRIETHYLSILANE CATALYZED BY PHOSPHINE-RHODIUM COMPLEXES [J].
BRADY, KA ;
NILE, TA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1981, 206 (03) :299-304
[5]  
Colvin E. W., 1988, SILICON REAGENTS ORG, P7
[6]  
CRABTREE RH, 1979, INORG SYNTH, V19, P218
[7]   ORGANOSILICON CHEMISTRY .22. CHLOROTRIS (TRIPHENYLPHOSPHINE) RHODIUM(I)-CATALYSIS OF REACTION BETWEEN HEX-1-YNE AND TRIETHYLSILANE [J].
DICKERS, HM ;
HASZELDINE, RN ;
MATHER, AP ;
PARISH, RV .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1978, 161 (01) :91-95
[8]   RHODIUM(II) PERFLUOROBUTYRATE CATALYZED HYDROSILYLATION OF 1-ALKYNES - TRANS ADDITION AND REARRANGEMENT TO ALLYLSILANES [J].
DOYLE, MP ;
HIGH, KG ;
NESLONEY, CL ;
CLAYTON, TW ;
LIN, J .
ORGANOMETALLICS, 1991, 10 (05) :1225-1226
[9]   HYDROSILYLATION OF PHENYLACETYLENE VIA AN OS(SIET3)(ETA-2-H2) INTERMEDIATE CATALYZED BY OSHCL(CO)(P(ISO-PR)3)2 [J].
ESTERUELAS, MA ;
ORO, LA ;
VALERO, C .
ORGANOMETALLICS, 1991, 10 (02) :462-466
[10]  
Fleming I., 1989, ORG REACTIONS, V37, P57
1234