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Stereoselective Formal Synthesis of (+)- and (−)-Cyclophellitol and (−)-Conduritol‑B and Synthesis of (−)-Conduramine‑B Derivative Using a Sulfinyl Moiety for C–O Bond Formation and α‑Chloro Sulfide for C–C Bond Formation
journal contribution
posted on 2016-04-20, 00:00 authored by Sadagopan Raghavan, Ravi Kumar Chiluveru, S. Ganapathy SubramanianThe formal total
synthesis of both the enantiomers of cyclophellitol
and conduritol-B and synthesis of conduramine-B derivative have been
achieved from a common intermediate, obtained by regio- and stereoselective
vicinal functionalization of a diene utilizing an intramolecular sulfinyl
group as a nucleophile, followed by stereoselective preparation of
an allylic sulfide by reaction of vinylzinc bromide with an electrophilic
α-chloro sulfide, and last by ring-closing metathesis reaction
as the key steps. The sulfoxide, sulfilimine, and sulfur ylid prepared
from this common intermediate have been transformed into derivatives
of conduritol-B, conduramine-B, and (−)-cyclophellitol, respectively.
The silyl sulfide was converted via sila-Pummerer rearrangement, hydrolysis,
and reduction in an one-pot operation to a hydroxymethyl group. [2,3]-Wittig–Still
rearrangement was employed for the synthesis of (+)-cyclophellitol.
The potential utility of sulfur intermediates as nucleophilic and
electrophilic partners in total synthesis is elegantly demonstrated.
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hydroxymethyl grouprearrangementstereoselective vicinal functionalizationFormationsulfur intermediatesintramolecular sulfinyl groupSulfinyl Moietycyclophellitolsilyl sulfideStereoselective Formal Synthesiselectrophilic partnersallylic sulfidesulfur ylidsynthesisstereoselective preparationvinylzinc bromideBond
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