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Concise Synthesis of Complicated Polypropionates through One‐Pot Dissymmetrical Two‐Directional Chain Elongation
Author(s) -
Exner Claudia J.,
Turks Maris,
Fonquerne Freddy,
Vogel Pierre
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003264
Subject(s) - stereocenter , desymmetrization , chemistry , aldol reaction , elongation , polyketide , chain (unit) , stereochemistry , combinatorial chemistry , enantioselective synthesis , organic chemistry , catalysis , materials science , physics , biosynthesis , astronomy , metallurgy , ultimate tensile strength , enzyme
Herein, a major breakthrough in a sulfur dioxide‐mediated oxyallylation cascade reaction is reported that allows the preparation of complex long‐chain polyketide fragments with more than ten stereogenic centers through a carefully designed desymmetrization process. An allylbissilane is combined, under the appropriate reaction conditions, with two different 1,3‐dioxy‐1,3‐dienes permitting the construction of a 13‐membered polypropionate precursor in one pot. Four stereocenters are selectively created during this process. The so‐obtained pseudo‐ C 2 ‐ or ‐ C S ‐symmetric products are desymmetrized through selective deprotection and can be selectively elongated in both directions using aldol chemistry.