DIASTEREOSELECTIVE REACTIONS OF TUNGSTEN ETA-2-PROPARGYL COMPLEXES WITH ALKYL-HALIDES AND ALDEHYDES

被引：35

作者：

COLLINS, MA ^{[1
]}

FENG, SG ^{[1
]}

WHITE, PA ^{[1
]}

TEMPLETON, JL ^{[1
]}

机构：

[1] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1992年 / 114卷 / 10期

关键词：

D O I：

10.1021/ja00036a028

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Deprotonation of the alkyne methyl group in Tp'(CO)(I)W (PhC = CCH3) [Tp' = hydridotris(3,5-dimethyl-pyrazolyl)borate] borate] produces a nucleophilic propargyl synthon. Reaction of the complex anion with MeI or PhCH2Br yields an elaborated alkyne and avoids the propargyl/allenyl regiochemical control problem. Deprotonation of Tp'(CO)(I)W(PhC = CCH2Me) followed by benzylation produces a single diastereomer as determined by H-1 NMR, while methylation of the anion formed from Tp'(CO)(I)W(PhC = CCH2Bz) yields the opposite diastereomer. Pivaldehyde or benzaldehyde adds to the coordinated eta-2-propargyl carbanion, Li[Tp'(CO)(I)W(eta-2-PhC = C = CHMe)], to form alcohol products. Conversion to a coordinated enyne was achieved for the benzaldehyde adduct by first forming the mesyl derivative and then eliminating HOSO2Me to yield Tp'(CO)(I)W(PhC = CCMe = CHPh).

引用

页码：3771 / 3775

页数：5

共 16 条

[1] METAL PERFLUOROALKANE-THIOLATES AND PERFLUOROARENE-THIOLATES .5. REACTIONS OF TRICARBONYL(PI-CYCLOPENTADIENYL)-MOLYBDENUM AND TRICARBONYL(PI-CYCLOPENTADIENYL)-TUNGSTEN THIOLATES AND ACETYLENES [J].