Copper‐Catalysed Rearrangement of Cyclic Ethynylethylene Carbonates: Synthetic Applications and Mechanistic Studies.

Autor:	Xu, Chao, Zhang, Hao, Lan, Shouang, Liu, Jinggong, Yang, Shuang, Zhang, Qi, Fang, Xinqiang
Předmět:	PROTON transfer reactions YLIDES NUCLEOPHILES KETONES ALLYLIC amination PHOSPHORUS CARBONATES
Zdroj:	Angewandte Chemie; 3/27/2023, Vol. 135 Issue 14, p1-13, 13p
Abstrakt:	Transition‐metal‐catalysed reactions of cyclic ethynylethylene carbonates have been intensively studied because of their robustness in new bond formation and diversified molecule construction. Known reaction modes usually involve a substitution step occurring at either the propargylic or terminal alkyne positions. Here, we report an unprecedented reaction pattern in which cyclic ethynylethylene carbonates first undergo a rearrangement to release allenal intermediates, which subsequently react with diverse nucleophiles to furnish synthetically useful allylic and propargylic allenols, phosphorus ylides, and cyclopropylidene ketones through an addition process rather than a substitution pathway. The products enable various further transformations, and mechanistic studies and theoretical calculations reveal that the reaction does not proceed via a semipinacol type [1,2]‐hydride shift, but through base‐mediated deprotonation as the key step to induce the rearrangement. [ABSTRACT FROM AUTHOR]
Databáze:	Complementary Index
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