Oxaphospholes and bisphospholes from phosphinophosphonates and α,β-unsaturated ketones.

ABSTRACT: The reaction of a {W(CO)5 }-stabilized phosphinophosphonate 1, (CO)5 WPH(Ph)P(O)(OEt)2 , with ethynyl- (2 a-f) and diethynylketones (7-11, 18, and 19) in the presence of lithium diisopropylamide (LDA) is examined. Lithiated 1 undergoes nucleophilic attack in the Michael position of the acetylenic ketones, as long as this position is not sterically encumbered by bulky (iPr)3 Si substituents. Reaction of all other monoacetylenic ketones with lithiated 1 results in the formation of 2,5-dihydro-1,2-oxaphospholes 3 and 4. When diacetylenic ketones are employed in the reaction, two very different product types can be isolated. If at least one (Me)3 Si or (Et)3 Si acetylene terminus is present, as in 7, 8, and 19, an anionic oxaphosphole intermediate can react further with a second equivalent of

SUBMITTER: Arkhypchuk AI 

PROVIDER: S-EPMC4304286 | biostudies-literature | 2013 Oct

REPOSITORIES: biostudies-literature