RUTHENIUM-CATALYZED ADDITIONS TO ALKYNES - SYNTHESIS OF ACTIVATED ESTERS AND THEIR USE IN ACYLATION REACTIONS

被引:95
作者
BRUNEAU, C [1 ]
NEVEUX, M [1 ]
KABOUCHE, Z [1 ]
RUPPIN, C [1 ]
DIXNEUF, PH [1 ]
机构
[1] UNIV RENNES 1, CNRS, CHIM COORDINAT ORGAN LAB, CAMPUS BEAULIEU, F-35042 RENNES, FRANCE
关键词
D O I
10.1055/s-1991-20866
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Enol esters can be obtained in one step by direct addition of carboxylic acids to terminal alkynes in the presence of a ruthenium-phosphine catalyst of type RuCl2(PR3)(arene). The presence of a nucleophilic phosphine allows the addition of the carboxylate group to the substituted alkyne carbon with high regioselectivity. From hex-1-yne or propyne, enol esters can be obtained with a variety of carboxylic acids including N-protected alpha-amino acids. Alkenylacetylene derivatives are thus precursors of 2-acyloxy-1,3-dienes. Ruthenium-catalysed addition of carboxylic acids and N-protected alpha-amino acids to propargyl alcohol derivatives gives rise to the synthesis of beta-oxopropyl esters. These enol esters and beta-oxopropyl esters are shown to be efficient acylating reagents under mild conditions to produce optically active amides or dipeptides. Especially stable enol formates allow access at 25-degrees-C to a variety of formamides and alpha-formylamino esters and in the presence of imidazole as a catalyst, they react with functionalised alcohols to give formates. Enol oxalates are shown to give access to alpha-dioxo derivatives via acylation of ammonia, amines, and unsaturated alcohols.
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页码:755 / 763
页数:9
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