Issue 13, 2022

THF-enabled PtBr2-catalyzed desymmetric hydrogenative [3 + 2] cycloaddition of 2-alkynylbenzaldehyde-tethered cyclohexadienones

Abstract

A THF-enabled PtBr2-catalyzed desymmetric hydrogenative [3 + 2] cycloaddition of 2-alkynylbenzaldehyde-tethered cyclohexadienones has been developed. The protocol provides a highly functionalized 6-7-6 polycyclic skeleton with four contiguous stereocenters in good to excellent yields of up to 97% yield and with exclusive exo-selectivity. The suggested cascade reaction pathway delineates a rare instance in platinum catalysis of the involvement of an in situ formed Pt-bound benzopyrylium species that participates in a Huisgen-type [3 + 2] cycloaddition with an electron-deficient alkene tether in the highly reactive organometallic intermediate. It also offers the first example of a metallocarbene species generated in this manner which undergoes hydrogenation with THF as the hydride transfer source. The synthetic utility of the catalytic method was exemplified by the late-stage stereoselective modification of the steroids estrone and estradiol under mild reaction conditions.

Graphical abstract: THF-enabled PtBr2-catalyzed desymmetric hydrogenative [3 + 2] cycloaddition of 2-alkynylbenzaldehyde-tethered cyclohexadienones

Associated articles

Supplementary files

Article information

Article type
Research Article
Submitted
12 Apr 2022
Accepted
22 May 2022
First published
23 May 2022

Org. Chem. Front., 2022,9, 3577-3584

THF-enabled PtBr2-catalyzed desymmetric hydrogenative [3 + 2] cycloaddition of 2-alkynylbenzaldehyde-tethered cyclohexadienones

R. Hu, J. Chen, Z. Wang, D. Shang, L. Yu, P. W. H. Chan and W. Rao, Org. Chem. Front., 2022, 9, 3577 DOI: 10.1039/D2QO00593J

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