Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations

The Journal of Organic Chemistry
Bo-Xiao TangJin-Heng Li

Abstract

A new, general method for the synthesis of spiro[4,5]trienones is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the (18)O-labeling experiments and DFT calculations.

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Citations

May 21, 2016·Chemical Reviews·Indranirekha SaikiaProdeep Phukan
Jun 18, 2017·The Journal of Organic Chemistry·Chada Raji ReddyKamalkishor Warudikar
Mar 25, 2017·Organic & Biomolecular Chemistry·Chada Raji ReddyBilla Bhargava Rao
Jan 25, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Xiang PengLuo Yang
Jul 6, 2016·Chemistry : a European Journal·Xiao-Wei LiangShu-Li You
Sep 19, 2012·Organic & Biomolecular Chemistry·Adeline Palisse, Stefan F Kirsch
Sep 16, 2020·Chemical Communications : Chem Comm·Akshay M NairChandra M R Volla
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Dec 21, 2013·The Journal of Organic Chemistry·Jordan D GoodreidRobert A Batey
Dec 11, 2019·The Journal of Organic Chemistry·Yu-Chao WangGuanyinsheng Qiu

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