Mechanistic Understanding of the Divergent Cyclizations of o‐Alkynylbenzaldehyde Acetals and Thioacetals Catalyzed by Metal Halides |
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| Authors: | Yanhua Mi Tao Zhou Kung‐Pern Wang Prof Daesung Lee Prof Yuanzhi Xia |
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| Affiliation: | 1. College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035 (P. R. China);2. Department of Chemistry, University of Illinois at Chicago, West Taylor Street, Chicago, IL 60607 (USA) |
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| Abstract: | The mechanisms of regiodivergent cyclizations of o‐alkynylbenzaldehyde acetals and thioacetals catalyzed by Pd and Pt halides are studied. DFT calculations found that both reactions are initiated by electrophilic activation of the acetylenic moiety instead of the previously proposed metal‐triggered C?X (X=O, S) cleavage. Both the regioselective cyclization of the π‐alkyne complex and the chemoselective 1,2]‐migration in the carbenoid intermediate were determined as key steps to achieving the observed divergence. For acetal derivatives containing an internal alkyne, the 6‐endo‐dig cyclization is more favorable and leads to the carbenoid intermediate easily through further steps of C?X fragmentation and carbocation cyclization. Then, from the carbenoid intermediate, the 1,2]‐migration of sulfur is easier than that of H, Me, and Ph; whereas, a reversed aptitude was predicted for the oxygen analogue, which is consistent with the greater ability of sulfur atoms to stabilize β‐carbocations. However, for precursors containing a terminal alkyne, the 5‐exo‐dig pathway is preferred and only the 1,2‐disubstituted indene product is seen, irrespective of the nature of the acetal; thus, a different product from that reported in the literature is predicted for benzaldehyde acetal with a terminal alkyne at the ortho position. This prediction led us to reconsider some of the reported results and hidden realities were uncovered with solid new experimental evidence. |
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| Keywords: | 1 2‐migration alkynes carbenoids cyclization metal halides |
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