Spontaneous dimerization of allenes in situ: an efficient synthesis of substituted 1,2-dimethylenecyclobutanes with high regio- and stereoselectivities

Maozhong Miao; Wenmin Wang; Weijun Yang; Lijun Xu; Jing Ma; Hongjun Ren

doi:10.1002/chem.201502503

Spontaneous dimerization of allenes in situ: an efficient synthesis of substituted 1,2-dimethylenecyclobutanes with high regio- and stereoselectivities

Chemistry. 2015 Oct 5;21(41):14447-53. doi: 10.1002/chem.201502503. Epub 2015 Aug 21.

Authors

Maozhong Miao¹, Wenmin Wang², Weijun Yang¹, Lijun Xu¹, Jing Ma³, Hongjun Ren⁴

Affiliations

¹ Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (P.R. China).
² Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University, Nanjing 210093, (P.R. China).
³ Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University, Nanjing 210093, (P.R. China). majing@nju.edu.cn.
⁴ Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (P.R. China). renhj@zstu.edu.cn.

PMID: 26385425
DOI: 10.1002/chem.201502503

Abstract

An intermolecular [2+2] cycloaddition reaction for the synthesis of 1,2-dimethylenecyclobutane derivatives from the commercially available starting materials aryl acetylenes, nBuLi, formamides, and trimethylsilyl cyanide (TMSCN) has been achieved. This reaction displays high regio- and stereoselectivities due to the captodative effect. The mechanism of the reaction has been investigated by the deuterium labeling experiments and DFT calculations.

Keywords: allenes; cycloaddition; density functional calculations; reaction mechanisms; stereoselectivity.