Investigation of the Origins of Regiochemical Control in [4+2] Cycloadditions of 2-Pyrones and Alkynylboronates

James D. Kirkham; Andrew G. Leach; Eleanor C. Row; Joseph P. A. Harrity

doi:10.1055/s-0031-1291142

Investigation of the Origins of Regiochemical Control in [4+2] Cycloadditions of 2-Pyrones and Alkynylboronates

James D. Kirkham, Andrew G. Leach, Eleanor C. Row, Joseph P. A. Harrity

Pharmacy

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Abstract

The [4+2] cycloaddition of 2-pyrones with substituted alkynylboronates has been studied. In general, the highest yielding cycloadditions were obtained in reactions that employed a trimethylsilyl-substituted alkynylboronate. The highest regioselectivities were obtained using the corresponding phenyl-substituted alkyne, which provided a single regioisomer irrespective of the 2-pyrone used. Mechanistic studies suggest that the high regioselectivity observed is due to stabilization of a zwitterionic transition state.

Original language	English
Pages (from-to)	1964-1973
Number of pages	10
Journal	SYNTHESIS-STUTTGART
Volume	44
Issue number	13
DOIs	https://doi.org/10.1055/s-0031-1291142
Publication status	Published - Jul 2012

Keywords

cycloaddition
Diels-Alder reaction
alkynes
boron
regioselectivity

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title = "Investigation of the Origins of Regiochemical Control in [4+2] Cycloadditions of 2-Pyrones and Alkynylboronates",

abstract = "The [4+2] cycloaddition of 2-pyrones with substituted alkynylboronates has been studied. In general, the highest yielding cycloadditions were obtained in reactions that employed a trimethylsilyl-substituted alkynylboronate. The highest regioselectivities were obtained using the corresponding phenyl-substituted alkyne, which provided a single regioisomer irrespective of the 2-pyrone used. Mechanistic studies suggest that the high regioselectivity observed is due to stabilization of a zwitterionic transition state.",

keywords = "cycloaddition, Diels-Alder reaction, alkynes, boron, regioselectivity",

author = "Kirkham, {James D.} and Leach, {Andrew G.} and Row, {Eleanor C.} and Harrity, {Joseph P. A.}",

year = "2012",

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T1 - Investigation of the Origins of Regiochemical Control in [4+2] Cycloadditions of 2-Pyrones and Alkynylboronates

AU - Kirkham, James D.

AU - Leach, Andrew G.

AU - Row, Eleanor C.

AU - Harrity, Joseph P. A.

PY - 2012/7

Y1 - 2012/7

N2 - The [4+2] cycloaddition of 2-pyrones with substituted alkynylboronates has been studied. In general, the highest yielding cycloadditions were obtained in reactions that employed a trimethylsilyl-substituted alkynylboronate. The highest regioselectivities were obtained using the corresponding phenyl-substituted alkyne, which provided a single regioisomer irrespective of the 2-pyrone used. Mechanistic studies suggest that the high regioselectivity observed is due to stabilization of a zwitterionic transition state.

AB - The [4+2] cycloaddition of 2-pyrones with substituted alkynylboronates has been studied. In general, the highest yielding cycloadditions were obtained in reactions that employed a trimethylsilyl-substituted alkynylboronate. The highest regioselectivities were obtained using the corresponding phenyl-substituted alkyne, which provided a single regioisomer irrespective of the 2-pyrone used. Mechanistic studies suggest that the high regioselectivity observed is due to stabilization of a zwitterionic transition state.

KW - cycloaddition

KW - Diels-Alder reaction

KW - alkynes

KW - boron

KW - regioselectivity

U2 - 10.1055/s-0031-1291142

DO - 10.1055/s-0031-1291142

M3 - Article

SN - 0039-7881

VL - 44

SP - 1964

EP - 1973

JO - SYNTHESIS-STUTTGART

JF - SYNTHESIS-STUTTGART

IS - 13

ER -

Investigation of the Origins of Regiochemical Control in [4+2] Cycloadditions of 2-Pyrones and Alkynylboronates

Abstract

Keywords

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