Synthesis of azasilacyclopentenes and silanols: Via Huisgen cycloaddition-initiated C-H bond insertion cascades

Jiun Le Shih; Santa Jansone-Popova; Christopher Huynh; Jeremy A. May

doi:10.1039/c7sc03130k

Synthesis of azasilacyclopentenes and silanols: Via Huisgen cycloaddition-initiated C-H bond insertion cascades

Jiun Le Shih, Santa Jansone-Popova, Christopher Huynh, Jeremy A. May

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

An unusual transition metal-free cascade reaction of alkynyl carbonazidates was discovered to form azasilacyclopentenes. Mild thermolysis afforded the products via a series of cyclizations, rearrangements, and an α-silyl C-H bond insertion (rather than the more common Wolff rearrangement, 1,2-shift, or β-silyl C-H insertion) to form silacyclopropanes. A mechanistic proposal for the sequence was informed by control experiments and the characterization of reaction intermediates. The substrate scope and post-cascade transformations were also explored.

Original language	English
Pages (from-to)	7132-7137
Number of pages	6
Journal	Chemical Science
Volume	8
Issue number	10
DOIs	https://doi.org/10.1039/c7sc03130k
State	Published - 2017
Externally published	Yes

Funding

The authors thank the Welch Foundation (grant E-1744) and the NSF (grant CHE-1352439) for funding. J.-L. S. is grateful to CBIP (UH) and the Studying Abroad Scholarship of Taiwan for fellowships. They are also grateful to Dr Ilja Popovs for discussion of the spectroscopic characterization of mechanistic intermediates.

Funders	Funder number
National Science Foundation	CHE-1352439
Directorate for Mathematical and Physical Sciences	1352439
Welch Foundation	E-1744

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abstract = "An unusual transition metal-free cascade reaction of alkynyl carbonazidates was discovered to form azasilacyclopentenes. Mild thermolysis afforded the products via a series of cyclizations, rearrangements, and an α-silyl C-H bond insertion (rather than the more common Wolff rearrangement, 1,2-shift, or β-silyl C-H insertion) to form silacyclopropanes. A mechanistic proposal for the sequence was informed by control experiments and the characterization of reaction intermediates. The substrate scope and post-cascade transformations were also explored.",

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T2 - Via Huisgen cycloaddition-initiated C-H bond insertion cascades

AU - Shih, Jiun Le

AU - Jansone-Popova, Santa

AU - Huynh, Christopher

AU - May, Jeremy A.

PY - 2017

Y1 - 2017

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AB - An unusual transition metal-free cascade reaction of alkynyl carbonazidates was discovered to form azasilacyclopentenes. Mild thermolysis afforded the products via a series of cyclizations, rearrangements, and an α-silyl C-H bond insertion (rather than the more common Wolff rearrangement, 1,2-shift, or β-silyl C-H insertion) to form silacyclopropanes. A mechanistic proposal for the sequence was informed by control experiments and the characterization of reaction intermediates. The substrate scope and post-cascade transformations were also explored.

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JO - Chemical Science

JF - Chemical Science

IS - 10

ER -

Synthesis of azasilacyclopentenes and silanols: Via Huisgen cycloaddition-initiated C-H bond insertion cascades

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