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Cover Picture: Mechanistic Understanding of the Divergent Cyclizations of o ‐Alkynylbenzaldehyde Acetals and Thioacetals Catalyzed by Metal Halides (Chem. Eur. J. 48/2015)
Author(s) -
Mi Yanhua,
Zhou Tao,
Wang KungPern,
Lee Daesung,
Xia Yuanzhi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201584801
Subject(s) - regioselectivity , carbenoid , chemistry , alkyne , catalysis , chemoselectivity , computational chemistry , combinatorial chemistry , organic chemistry , rhodium
For better understanding of the divergent regioselectivity in Pd‐ and Pt‐catalyzed cyclizations of o ‐alkynylbenzaldehyde acetals and thioacetals a comprehensive theoretical and experimental study has been carried out . It was found that both the initial regioselective cyclization of the π‐alkyne complex and the final chemoselective [1,2]‐migration of the carbenoid intermediate are important steps leading to the observed divergence. The insights obtained here could shed light on the understanding of related reactions and should be useful for designing new reactions. Moreover, this study represents a rare example in which the DFT predictions mandate the revision of existing experimental data. For more information see the Full Paper by D. Lee, Y. Xia et al. on page 17256 ff.