Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans: Scope and Mechanism

Christian A. Malapit; Sampada M. Chitale; Meena S. Thakur; Rosa Taboada; Amy R. Howell

doi:10.1021/acs.joc.5b00604

Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans: Scope and Mechanism

Christian A. Malapit, Sampada M. Chitale, Meena S. Thakur, Rosa Taboada, Amy R. Howell^*

^*Corresponding author for this work

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

19 Scopus citations

Abstract

A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by ¹³C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond of the cyclopropane to form a platinacyclobutane intermediate. To our knowledge, this is the first alkoxy-substituted platinacyclobutane that has been observed spectroscopically. The scope and a proposed mechanism of this new Pt-catalyzed transformation are described. (Chemical Equation Presented).

Original language	English (US)
Pages (from-to)	5196-5209
Number of pages	14
Journal	Journal of Organic Chemistry
Volume	80
Issue number	10
DOIs	https://doi.org/10.1021/acs.joc.5b00604
State	Published - May 15 2015
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

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title = "Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans: Scope and Mechanism",

abstract = "A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by 13C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond of the cyclopropane to form a platinacyclobutane intermediate. To our knowledge, this is the first alkoxy-substituted platinacyclobutane that has been observed spectroscopically. The scope and a proposed mechanism of this new Pt-catalyzed transformation are described. (Chemical Equation Presented).",

author = "Malapit, {Christian A.} and Chitale, {Sampada M.} and Thakur, {Meena S.} and Rosa Taboada and Howell, {Amy R.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

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T1 - Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans

T2 - Scope and Mechanism

AU - Malapit, Christian A.

AU - Chitale, Sampada M.

AU - Thakur, Meena S.

AU - Taboada, Rosa

AU - Howell, Amy R.

PY - 2015/5/15

Y1 - 2015/5/15

N2 - A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by 13C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond of the cyclopropane to form a platinacyclobutane intermediate. To our knowledge, this is the first alkoxy-substituted platinacyclobutane that has been observed spectroscopically. The scope and a proposed mechanism of this new Pt-catalyzed transformation are described. (Chemical Equation Presented).

AB - A novel Pt-catalyzed rearrangement of oxaspirohexanes to 3-methylenetetrahydrofurans is reported. Mechanistic studies by 13C-labeling experiments confirm oxidative addition of Pt(II) regioselectively to the least substituted carbon-carbon bond of the cyclopropane to form a platinacyclobutane intermediate. To our knowledge, this is the first alkoxy-substituted platinacyclobutane that has been observed spectroscopically. The scope and a proposed mechanism of this new Pt-catalyzed transformation are described. (Chemical Equation Presented).

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Pt-Catalyzed Rearrangement of Oxaspirohexanes to 3-Methylenetetrahydrofurans: Scope and Mechanism

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