Ruthenium-Catalysed Intermolecular [2 + 2] Cycloaddition of Unactivated Allenes and Alkynes with Unusual Regioselectivity

Title	Ruthenium-Catalysed Intermolecular [2 + 2] Cycloaddition of Unactivated Allenes and Alkynes with Unusual Regioselectivity
Authors	Chaoshen Zhang, Herman H. Y. Sung, Ian D. Williams, Yun-Dong Wu, Jianwei Sun
Magazine	Journal of the American Chemical Society
Date	09/08/2025
DOI	https://doi.org/10.1021/jacs.5c11285
Introduction	This study presents an effective method for intermolecular [2 + 2] cycloaddition, utilising unactivated and unsymmetrical allenes and alkynes, showcasing unusual regioselectivity by favouring the most sterically hindered isomer. The catalyst CpRu(MeCN)3PF6 proved exceptionally efficient, facilitating the synthesis of various 3-alkylidenecyclobutenes with diverse applications and excellent functional group tolerance. Experimental and DFT analyses offered valuable understanding of the mechanism, especially the atypical regioselectivity observed.
Quote	Chaoshen Zhang, Herman H. Y. Sung, Ian D. Williams, Yun-Dong Wu, Jianwei Sun. Ruthenium-Catalysed Intermolecular [2 + 2] Cycloaddition of Unactivated Allenes and Alkynes with Unusual Regioselectivity. J. Am. Chem. Soc. 2025. Vol. 147(37):33350-33358. DOI: 10.1021/jacs.5c11285
Element	Ruthenium (Ru)
Industry	Chemical & Pharmacy

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