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.

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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

N2 - 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.

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.

UR - https://www.scopus.com/pages/publications/85030088886

U2 - 10.1039/c7sc03130k

DO - 10.1039/c7sc03130k

M3 - Article

AN - SCOPUS:85030088886

SN - 2041-6520

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EP - 7137

JO - Chemical Science

JF - Chemical Science

IS - 10

ER -

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

Abstract

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