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. 2018 May 2;140(17):5860-5865.
doi: 10.1021/jacs.8b01813. Epub 2018 Apr 17.

Au-Catalyzed Intermolecular [2+2] Cycloadditions between Chloroalkynes and Unactivated Alkenes

Yu-Bin Bai  1   2 , Zaigang Luo  2 , Yuguang Wang  2 , Jin-Ming Gao  1 , Liming Zhang  2
Affiliations

Au-Catalyzed Intermolecular [2+2] Cycloadditions between Chloroalkynes and Unactivated Alkenes

Yu-Bin Bai et al. J Am Chem Soc. .

Abstract

The [2+2] cycloaddition is a versatile strategy for the synthesis of strained cyclobutenes of high synthetic value. In this study, two efficient intermolecular [2+2] cycloadditions between two different types of chloroalkynes and unactivated alkene are realized with gold catalysis. Of significance is that the reaction works with challenging monosubstituted unactivated alkenes, which is unprecedented in gold catalysis and scarcely documented in other metal-catalyzed/promoted reactions; moreover, the reaction exhibits excellent regioselectivities, which are much better than those reported in literature. With 1,2-disubstituted unactivated alkenes, the reaction is largely stereospecific. The cyclobutene products can be prepared in nearly gram scale and readily undergo further reactions including various cross-coupling reactions using the C(sp2)-Cl and/or C(sp2)-SPh bond, which in turn substantially broaden the scope of accessible cyclobutenes and enhance the synthetic utility of this bimolecular reaction.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
ORTEP drawing of 6f with 50% probability ellipsoids.
Scheme 1
Scheme 1
Catalytic Intermolecular [2+2] Cycloadditions of Alkynes with Alkenes
Scheme 2
Scheme 2
Proposed Reaction Mechanism
Scheme 3
Scheme 3
Transformations of 3aa
Scheme 4
Scheme 4
Transformations of 5a
See this image and copyright information in PMC

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