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Non‐Covalent Carbonyl‐Directed Heck–Matsuda Desymmetrizations: Synthesis of Cyclopentene‐Fused Spirooxindoles, Spirolactones, and Spirolactams
Author(s) -
Kattela Shivashankar,
Heerdt Gabriel,
Correia Carlos R. D.
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600946
Subject(s) - chemistry , enantiomer , enantioselective synthesis , cyclopentene , heck reaction , covalent bond , carbonyl group , combinatorial chemistry , organic chemistry , stereochemistry , catalysis , palladium
Enantioselective carbonyl‐directable Heck reactions using aryldiazonium salts were developed with the aim to construct chiral quaternary spiro centers in an efficient manner. Five‐ and six‐membered spirooxindoles, spirolactones, and spirolactams (36 examples) were obtained in good to excellent isolated yields with diastereoselectivities ranging from 13:1 to >20:1, and enantiomeric excesses up to 99% in short reaction times (1.0–1.5 h) under mild conditions (40 °C). A rationale for the diastereo‐ and enantioselectivity based on an unprecedented non‐covalent carbonyl group directing effect is also presented, and supported by computational calculations.