Carbonyl Phosphorylation via N,3E>-Bifunctional Reagents. Probing Mechanistic and Reactivity Features through Chemical and Isotopic Labelling

DOI: 10.1039/P19940003169

Source and publish data:

Journal of the Chemical Society. Perkin transactions I p. 3169 - 3182 (1994)

Update date:2022-08-05

Topics:

Authors:

Devitt, Paul G.

Kee, Terence P.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/P19940003169

A range of organophosphorus(III) esters of the general form PX(SiR3)n has been prepared via reaction of PCl with R3SiOH or LiN(SiMe3)2 respectively.These esters will phosphonylate aldehydes via the Abramov reaction to afford α-siloxyphosphonate esters cleanly and in high yields.The mechanism of the Abramov reaction using POSiR3 reagents has been investigated by (i) 18O isotopic labelling experiments which reveal that reaction proceeds with exclusive rather than bond cleavage which, in turn, supports a mechanism with overall retention of configuration at phosphorus, (ii) double crossover experiments which support intramolecular silyl group transfer and (iii) manipulations of the electron-donating properties of the carbonyl substrate which suggest that bond formation is rate determining.Further tuning of the phosphonylation reaction is possible by manipulating (a) the nature of the phosphorus-coordinated donor atoms in the chelate ring, (b) the size and rigidity of the chelate ring, (c) the ester residue donor atom X and (d) the silicon substituents R.

Full text of DOI:10.1039/P19940003169

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:1,3-Dimethyl-2-triphenylsilanyloxy-[1,3,2]diazaphospholidine

Cas No:160622-54-8

R&D Labs maybe for 160622-54-8

SHAANXI TOP PHARM CHEMICAL CO.LTD

Contact:+86-029-85733403

Address:No.108 ,west sector,south er huan,xi'an,china
Anhui Asahikasei Chemical Co., Ltd

Contact:86-551-4259770

Address:No. 88 Linquan Road Hefei Anhui China
SunaTech Inc.

Contact:+86 512 6287 2180

Address:398 Ruoshui Road, Suzhou Industrial Park, Suzhou, Jiangsu, P. R. China
SHAANXI FUJIE PHARMACEUTICAL CO.,LTD

website:http://www.fujiepharm.com

Contact:+86-29-63650906

Address:Yuanqu Yi Road, Qinghe Food Industrial Park, Sanyuan County, Shaanxi Province, China
nanjing suru chemical co.ltd

Contact:+86-025-52406782

Address:8 Taizishan Rd., Yanjiang Industrial Development Area, Nanjing, Jiangsu, China.

Relevant to this article

Complexation-induced inversion of helicity by an organic guest in a dynamic molecular propeller based on a tristerephthalamide host with a two-layer structure

Doi:10.1039/c4cc00323c
(2014)
Reactions of 2-chloro-4-methylquinolines with sulfur nucleophiles and of 4-methylquinoline-2(1H)-thiones with substituted benzyl chlorides

Doi:10.1134/S1070428014030257
()
The thermal and mass spectral fragmentation of N-butyl thiolo-, thiono-, and dithio-chloroformate

Doi:10.1080/10426507.2011.582801
(2011)
Alkyne complexes of copper(I) (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato): Syntheses and characterization of (η²-bis(trimethylsilyl)acetylene) copper(I) (hfac), (μ-η¹-bis(trimethylsilyl)acetylene) bis(copper(I) (hfac)) and a series of (η²-alkyne) Cu(hfac) complexes

Doi:10.1016/0022-328X(96)06113-X
(1996)
Design, synthesis and biological evaluation of small-azo-dyes as potent Vesicular Glutamate Transporters inhibitors

Doi:10.1016/j.ejmech.2014.03.056
(2014)
Microbial transformations of buagarofuran, an anti-anxietic agent

Doi:10.1016/j.tet.2014.04.011
(2014)

Article Doi