REACTIONS BETWEEN TANTALUM ALKYNE OR NIOBIUM ALKYNE COMPLEXES AND CARBONYL-COMPOUNDS

被引：67

作者：

KATAOKA, Y ^{[1
]}

MIYAI, J ^{[1
]}

OSHIMA, K ^{[1
]}

TAKAI, K ^{[1
]}

UTIMOTO, K ^{[1
]}

机构：

[1] KYOTO UNIV,FAC ENGN,DEPT IND CHEM,YOSHIDA,KYOTO 60601,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1992年 / 57卷 / 07期

关键词：

D O I：

10.1021/jo00033a015

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A variety of tantalum-alkyne complexes are generated in situ by treatment of alkynes with low-valent tantalum derived from TaCl5 and zinc. These complexes add regioselectively to carbonyl compounds in a one-to-one fashion to yield (E)-allylic alcohols stereoselectively. Iodinolysis of the oxatantalacyclopentene, which is postulated as an intermediate of the reaction, gives a (Z)-3-iodo-2-propen-1-ol derivation. In contrast to tantalum-alkyne complexes, niobium-alkyne complexes, prepared with low-valent niobium derived from NbCl5 and zinc, add in situ to aldehydes in a one-to-two fashion to give 1,3-diene derivatives. The dienes are produced through (i) addition of the alkyne complexes with 2 equiv of aldehydes at cis vicinal positions of the alkenes and (ii) deoxygenative elimination of 2,7-dioxanioba-4-cycloheptene complexes.

引用

页码：1973 / 1981

页数：9

共 63 条

[1] ACETYLENE DERIVATIVES OF TITANOCENE
ALT, HG
ENGELHARDT, HE
RAUSCH, MD
KOOL, LB
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (12) : 3717 - 3718
[2] STABILIZATION OF SMALL-RING ACETYLENES BY COMPLEX FORMATION WITH PLATINUM
BENNETT, MA
ROBERTSO.GB
WHIMP, PO
YOSHIDA, T
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (15) : 3797 - &
[3] METAL-COMPLEXES OF SMALL CYCLOALKYNES AND ARYNES
BENNETT, MA
SCHWEMLEIN, HP
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1989, 28 (10) : 1296 - 1320
[4] Brandsma L., 1988, PREPARATIVE ACETYLEN
[5] ALKYNE CYCLIZATIONS AT REDUCED TANTALUM CENTERS - SYNTHESIS AND MOLECULAR-STRUCTURE OF (ETA-6-C6ME6)TA(O-2,6-I-PR2C6H3)2CL
BRUCK, MA
COPENHAVER, AS
WIGLEY, DE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) : 6525 - 6527
[6] GROUP-4 METAL-COMPLEXES OF BENZYNES, CYCLOALKYNES, ACYCLIC ALKYNES, AND ALKENES
BUCHWALD, SL
NIELSEN, RB
[J]. CHEMICAL REVIEWS, 1988, 88 (07) : 1047 - 1058
[7] SYNTHESIS, REACTIONS, AND X-RAY CRYSTAL-STRUCTURE DETERMINATION OF CP2HF(ISOBUTYLENE).PME3
BUCHWALD, SL
KREUTZER, KA
FISHER, RA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (11) : 4600 - 4601
[8] THE SYNTHESIS, REACTIONS, AND MOLECULAR-STRUCTURE OF ZIRCONOCENE ALKYNE COMPLEXES
BUCHWALD, SL
WATSON, BT
HUFFMAN, JC
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) : 2544 - 2546
[9] BUCHWALD SL, 1986, J AM CHEM SOC, V108, P741
[10] COMPLEXES OF ACETYLENES WITH PLATINUM(II) .1. ALKYNES
CHATT, J
GUY, RG
DUNCANSON, LA
[J]. JOURNAL OF THE CHEMICAL SOCIETY, 1961, (MAR): : 827 - &

← 1 2 3 4 5 6 7 →