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Unexpected Selectivity in Sodium Borohydride Reductions of α‐Substituted Esters: Experimental and Theoretical Studies
Author(s) -
Li LiangChun,
Jiang JuXing,
Ren Jie,
Ren Yi,
Pittman Charles U.,
Zhu HuaJie
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500824
Subject(s) - chemistry , sodium borohydride , hydride , selectivity , medicinal chemistry , borohydride , organic chemistry , hydrogen , catalysis
Abstract The propensity of sodium borohydride to reduce the carbonyl group in eleven α‐substituted and two aromatic esters has been investigated by experiments and at the B3LYP/6‐31++G(d,p)//HF/6‐31G(d,p) level of theory. The chemoselectivities in nine of these reductions have been examined by experiments. Experimental results agree well with the calculated order of activation energies for hydride transfer to the ester carbonyl group. Methyl α‐bromoacetate reduces faster than methyl α‐fluoroacetate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)