A new simple method for the synthesis of 1-alkynylphosphonates using (EtO)2P(O)CCl3 as precursor

Abstract

1-Alkynylphosphonates 4 were obtained from (EtO) 2 P(O)CCl 3 1 and aldehydes in a one-pot procedure. It involves the formation of α-chlorovinyl phosphonate intermediates 3 by a Peterson olefination reaction followed by dehydrochlorination with LiHMDS.

Topochemical mechanoactivated phosphonylethynylation of pyrroles with chloroethynylphosphonates on solid Al2O3 or K2CO3 media

“…14 To the best of our knowledge, ethynylphosphonates containing pyrrole moieties are almost unknown, and only one paper describing the synthesis of 2-(N-methylpyrrol-2-yl)ethynylphosphonate from (EtO) 2 P(O)CCl 3 and pyrrole-2-carbaldehyde has been reported. 15 This method involves the formation of α-chlorovinylphosphonate via a Peterson olefination reaction followed by dehydrochlorination with LiHMDS (Scheme 1). Scheme 1.…”

An efficient and recyclable silica‐supported carbene–Cu(II) catalyst for the oxidative coupling reaction of terminal alkynes with H‐phosphonates under base‐free reaction conditions

“…Diethyl[(phenyl)ethynyl]phosphonate ( 6a ), diethyl[(4‐methylphenyl)ethynyl]phosphonate ( 6b ), diethyl[(4‐methoxylphenyl)ethynyl]phosphonate ( 6 d ), diethyl[(4‐fluorophenyl)ethynyl]phosphonate ( 6e ), [diethyl(4‐chlorophenyl)ethynyl]phosphonate ( 6f ), diethyl[(3‐aminophenyl)ethynyl]phosphonate ( 6 h ), diethyl[(4‐phenylphenyl)ethynyl]phosphonate ( 6j ), diethyl(3‐pyridinylethynyl)phosphonate ( 6 k ), di(isopropyl)[(phenyl)ethynyl]phosphonate ( 6 l ), diethyl‐1‐heptynylphosphonate ( 6 m ), diethyl‐1‐hexynylphosphonate ( 6n ), diethyl‐3‐(benzyloxy)‐1‐propynylphosphonate ( 6o ), and diethyl(ethoxycarbonyl)phosphonate ( 6p ), have been characterized by comparing their 1 H and 13 C spectral data (see Supporting Information) with those reported in the literature.…”

Controlled Reactivity of Phosphonates by Temporary Silicon Connection

“…When the carbonyl compound is an aromatic or heteroaromatic aldehyde, diethyl 1-alkenylphosphonates 25 are readily converted into diethyl 1-alkynylphosphonates 26 in high yields (87-96%) in a one-pot process by treatment at low temperature with LiHMDS or LDA and subsequent elimination of LiCl (Scheme 11). 54 This class of 1-alkynylphosphonates 26 is difficult to prepare by other methods which, generally, are depending on the availability of the terminal alkyne.…”