Intramolecular [4+2]-cycloadditions of nitroalkenes with olefins. 2

Scott E. Denmark; Young Choon Moon; Christopher J. Cramer; Michael S. Dappen; C. B.W. Senanayake

doi:10.1016/S0040-4020(01)89054-2

Intramolecular [4+2]-cycloadditions of nitroalkenes with olefins. 2

Scott E. Denmark, Young Choon Moon, Christopher J. Cramer, Michael S. Dappen, C. B.W. Senanayake

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Abstract

The intramolecular [4+2]-cycloadditions of di- and trisubstituted nitroalkenes with unactivated olefins are described. The cycloadditions proceed readily at low temperatures in the presence of SnCl₄. The reactions are shown to be stereospecific in the preservation of dienophile configuration in the product. The configuration of the heterodiene controls the stereochemistry of the ring fusion but the selectivity is high only with trisubstituted nitroalkenes. The rate of cycloaddition of a cis dienophile is ca. 20-fold faster than a trans dienophile. The implications for mechanism and transition structure are discussed.

Original language	English (US)
Pages (from-to)	7373-7392
Number of pages	20
Journal	Tetrahedron
Volume	46
Issue number	21
DOIs	https://doi.org/10.1016/S0040-4020(01)89054-2
State	Published - 1990

Bibliographical note

Funding Information:
Acknowledgements. We gratefully acknowledge the financial support provided by the National Instituteso f Health (PHS GM-30938). M.S.D. and Y.-CM. acknowledge the University of Illinois for Graduate Fellowships. C.J.C thanks the National Science Foundation for a GraduateF ellowship (1984-1987). S.E.D. also acknowledgess upportf orm the NSF (PresidentialY oung InvestigatorA ward (19851990) and the Alfred P. Sloan Foundation (198%1 989).

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title = "Intramolecular [4+2]-cycloadditions of nitroalkenes with olefins. 2",

abstract = "The intramolecular [4+2]-cycloadditions of di- and trisubstituted nitroalkenes with unactivated olefins are described. The cycloadditions proceed readily at low temperatures in the presence of SnCl4. The reactions are shown to be stereospecific in the preservation of dienophile configuration in the product. The configuration of the heterodiene controls the stereochemistry of the ring fusion but the selectivity is high only with trisubstituted nitroalkenes. The rate of cycloaddition of a cis dienophile is ca. 20-fold faster than a trans dienophile. The implications for mechanism and transition structure are discussed.",

author = "Denmark, {Scott E.} and Moon, {Young Choon} and Cramer, {Christopher J.} and Dappen, {Michael S.} and Senanayake, {C. B.W.}",

note = "Funding Information: Acknowledgements. We gratefully acknowledge the financial support provided by the National Instituteso f Health (PHS GM-30938). M.S.D. and Y.-CM. acknowledge the University of Illinois for Graduate Fellowships. C.J.C thanks the National Science Foundation for a GraduateF ellowship (1984-1987). S.E.D. also acknowledgess upportf orm the NSF (PresidentialY oung InvestigatorA ward (19851990) and the Alfred P. Sloan Foundation (198%1 989).",

year = "1990",

doi = "10.1016/S0040-4020(01)89054-2",

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T1 - Intramolecular [4+2]-cycloadditions of nitroalkenes with olefins. 2

AU - Denmark, Scott E.

AU - Moon, Young Choon

AU - Cramer, Christopher J.

AU - Dappen, Michael S.

AU - Senanayake, C. B.W.

N1 - Funding Information: Acknowledgements. We gratefully acknowledge the financial support provided by the National Instituteso f Health (PHS GM-30938). M.S.D. and Y.-CM. acknowledge the University of Illinois for Graduate Fellowships. C.J.C thanks the National Science Foundation for a GraduateF ellowship (1984-1987). S.E.D. also acknowledgess upportf orm the NSF (PresidentialY oung InvestigatorA ward (19851990) and the Alfred P. Sloan Foundation (198%1 989).

PY - 1990

Y1 - 1990

N2 - The intramolecular [4+2]-cycloadditions of di- and trisubstituted nitroalkenes with unactivated olefins are described. The cycloadditions proceed readily at low temperatures in the presence of SnCl4. The reactions are shown to be stereospecific in the preservation of dienophile configuration in the product. The configuration of the heterodiene controls the stereochemistry of the ring fusion but the selectivity is high only with trisubstituted nitroalkenes. The rate of cycloaddition of a cis dienophile is ca. 20-fold faster than a trans dienophile. The implications for mechanism and transition structure are discussed.

AB - The intramolecular [4+2]-cycloadditions of di- and trisubstituted nitroalkenes with unactivated olefins are described. The cycloadditions proceed readily at low temperatures in the presence of SnCl4. The reactions are shown to be stereospecific in the preservation of dienophile configuration in the product. The configuration of the heterodiene controls the stereochemistry of the ring fusion but the selectivity is high only with trisubstituted nitroalkenes. The rate of cycloaddition of a cis dienophile is ca. 20-fold faster than a trans dienophile. The implications for mechanism and transition structure are discussed.

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EP - 7392

JO - Tetrahedron

JF - Tetrahedron

IS - 21

ER -

Intramolecular [4+2]-cycloadditions of nitroalkenes with olefins. 2

Abstract

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