Photo-Arbuzov rearrangements of cyclic phosphite systems
نویسندگان
چکیده
The direct UV irradiation of cyclic phosphites 1–4 was carried out in argon-saturated solvents. In all cases examined, the rearranged, ring-contracted Photo-Arbuzov phosphonate was the major product formed with isolated yields ranging from 40 to 50%. These phosphonate photoproducts, 5–8, represent novel, bicyclic, aromatic phosphonate systems never before described in the literature of heterocyclic phosphorus chemistry. These compounds are of interest based on their potential application as ring-constrained, non-hydrolyzable mimics of phosphorylated tyrosine. © 2002 Elsevier Science B.V. All rights reserved.
منابع مشابه
Crystal structure of ethyl 2-(diethoxyphosphoryl)-2-(2,3,4-trimethoxyphenyl)acetate
The title compound, C17H27O8P, was prepared by Michaelis-Arbuzov reaction of ethyl 2-bromo-2-(2,3,4-tri-meth-oxy-phen-yl)acetate and triethyl phosphite. Such compounds rarely crystallize, but single crystals were recovered after the initial oil was left for approximately 10 years. The bond angle of the sp (3)-hybridized C atom connecting the benzene derivative with the phospho unit is widened m...
متن کاملSynthesis of novel pyrophosphorothiolate-linked dinucleoside cap analogues in a ball mill.
Michaelis-Arbuzov reactions of S-aryl disulfide derivatives of 3'-thiothymidine or 5'-thioadenosine with tris(trimethylsilyl) phosphite proceeded in high yields to the corresponding phosphorothiolate monoesters. Subsequent hydrolytic desilylation and phosphate coupling were effected in one-pot using liquid-assisted grinding in a vibration ball mill. Novel 3',5'- and 5',5'-pyrophosphorothiolate-...
متن کاملEnantioselective dearomatization of isoquinolines by anion-binding catalysis en route to cyclic α-aminophosphonates.
An enantioselective dearomatization of isoquinolines has been developed using chiral anion-binding catalysis. This transformation, catalyzed by a simple and easy to prepare tert-leucine-based thiourea derivative, makes use of silyl phosphite as a nucleophile and generates cyclic α-aminophosphonates. This is the first time asymmetric anion-binding catalysis has been applied to the synthesis of α...
متن کاملHexachloroacetone as a precursor for a tetrachloro-substituted oxyallyl intermediate: [4+3] cycloaddition to cyclic 1,3-dienes.
The enol phosphate 2,2-dichloro-1-(trichloromethyl)ethenyl diethyl phosphate (1), easily available by a Perkow reaction between hexachloroacetone and triethyl phosphite, reacts with sodium trifluoroethoxide/trifluoroethanol in the presence of cyclic 5-membered 1,3-dienes to furnish alpha,alpha,alpha',alpha'-tetrachloro-substituted[3.2.1]bicyclic ketones 2. A [4+3] cycloaddition of a tetrachloro...
متن کاملPreparation of potential cell-permeant nucleoside-2',3'-cyclic phosphate precursors.
Uridine-3'-phosphorothiolate triesters bearing lipophilic moieties were prepared via Michaelis-Arbuzov chemistry. Subsequent deprotection of the S-cholesteryl phosphorothiolate triester afforded the corresponding diester which underwent spontaneous Cyclization to cleanly afford uridine 2',3'-cyclic phosphate. This transesterification reaction could be expedited by treatment with iodine under mi...
متن کامل