1335101-40-0Relevant articles and documents
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
Raghavan, Sadagopan,Chiluveru, Ravi Kumar,Ganapathy Subramanian
, p. 4252 - 4261 (2016)
The 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.
Toward a modular, bidirectional synthesis of (-)-mucocin
Raghavan, Sadagopan,Subramanian, S. Ganapathy
, p. 7529 - 7539 (2011/10/12)
A convergent stereoselective synthesis of the C13-C34 fragment of (-)-mucocin is described. The salient features include (a) the bidirectional synthesis of the C-2 symmetric C13-C21 subunit, (b) regio- and stereoselective preparation of a 1,3-diol derivative from a diene activated by NBS via intramolecular nucleophilic sulfinyl group participation, (c) utilizing the self-metathesis reaction to prepare a functionalized C10 alkene, and (d) regio- and stereoselective intermolecular epoxide opening to construct the ether bond between C20 and C24. An organocatalytic α-hydoxylation has been employed to create the C4 stereogenic center of C1-C12 subunit. Attempted union of the two subunits utilizing the B-alkyl Suzuki coupling did not succeed.
