In:
Canadian Journal of Chemistry, Canadian Science Publishing, Vol. 77, No. 7 ( 1999-07-01), p. 1274-1280
Abstract:
The parent phostone, 2-ethoxy-1,2-oxaphosphorinane 2-oxide 1, and derivatives with substituents at the 3-position (methyl, phenyl, and benzyl; compounds 2-4) were converted with Lawesson's reagent to provide the corresponding sulfide analogues 5-8 in moderate yields. The conversion of 2-4 occurred with retention of configuration at the phosphorus center. This was implied from the relative R f values and 13 C and 31 P NMR chemical shifts of the individual isomers and confirmed for the transformation of 3b to 7b by X-ray structures of each of these. Oxidation of 7b, 8a, and 8b with m-chloroperoxybenzoic acid alone led to the corresponding oxides 3b, 4a, and 4b with retention. The presence of trifluoroacetic acid during this oxidation process led to varying degrees of epimerization about phosphorus and was dependent on the relative molar equivalents of this acid.Key words: 2-ethoxy-1,2-oxaphosphorinane 2-oxide, 2-ethoxy-1,2-oxaphosphorinane 2-sulfide, phostone, thiophostone, Lawesson's reagent, stereoselective synthesis, X-ray diffraction.
Type of Medium:
Online Resource
ISSN:
0008-4042
,
1480-3291
Language:
English
Publisher:
Canadian Science Publishing
Publication Date:
1999
detail.hit.zdb_id:
1482256-8
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