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The Effect of Sulfoxides on the Stereoselective Construction of Tetrahydrofurans: Total Synthesis of (+)‐Goniothalesdiol
Author(s) -
HernándezTorres Gloria,
Carreño M. Carmen,
Urbano Antonio,
Colobert Françoise
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.201002637
Subject(s) - stereoselectivity , total synthesis , chemistry , stereochemistry , organic chemistry , catalysis
Good to excellent stereoselectivities were achieved in the reductive cyclization (with Et 3 SiH/trimethylsilyl trifluoromethanesulfonate (TMSOTf)) of enantiopure hydroxy sulfinyl ketones en route to 2,5‐ cis ‐disubstituted tetrahydrofuran skeletons. Electrostatic effects of the exocyclic sulfoxide, which stabilized the reactive intermediate oxocarbenium conformations, were responsible for the observed stereocontrol. A model is proposed to explain the results. The use of this reaction and the asymmetric β‐ketosulfoxide reduction as key steps facilitated the total enantioselective synthesis of the natural β‐C‐aryl glycoside (+)‐goniothalesdiol.