(η5-C5H5)Fe(CO)2(η1-C5R5). A Useful Synthetic Equivalent of 5-Amino-1,3-cyclopentadiene in Cycloaddition Reactions

Richard S. Glass; Wesley W. McConnell; Stephen W. Andruski

doi:10.1021/jo00376a012

(η⁵-C₅H₅)Fe(CO)₂(η¹-C₅R₅). A Useful Synthetic Equivalent of 5-Amino-1,3-cyclopentadiene in Cycloaddition Reactions

Richard S. Glass, Wesley W. McConnell, Stephen W. Andruski

Chemistry and Biochemistry

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

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Abstract

Diels-Alder reactions of 5-amino- 1,3-cyclopentadiene have not been reported, and other stereoselective, high-yield routes to substituted bicyclo[2.2.1]hept-2-en-7-syn-amines are limited. This paper reports use of (n⁵-C₅H₅)Fe-(CO)₂(n¹-C₅H₅) (1) as a synthetic equivalent of 5-amino-1,3-cyclopentadiene in cycloaddition reactions. The previously reported cycloadducts of 1 and alkenes were treated with ammonium cerium(IV) nitrate, bromine, or chlorine in acetonitrile containing sodium azide to give the corresponding acyl azides in which the CON₃ group replaced the (n⁵-C₅H₅)Fe(CO)₂ group with retention of stereochemistry in good yield. Thermal Curtius rearrangement of these acyl azides proceeded stereospecifically in excellent yield. This regioselective and stereoselective sequence provides a useful route to substituted 7-syn-amino-2-norbornenes.

Original language	English (US)
Pages (from-to)	5123-5127
Number of pages	5
Journal	Journal of Organic Chemistry
Volume	51
Issue number	26
DOIs	https://doi.org/10.1021/jo00376a012
State	Published - 1986

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Organic Chemistry

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title = "(η5-C5H5)Fe(CO)2(η1-C5R5). A Useful Synthetic Equivalent of 5-Amino-1,3-cyclopentadiene in Cycloaddition Reactions",

abstract = "Diels-Alder reactions of 5-amino- 1,3-cyclopentadiene have not been reported, and other stereoselective, high-yield routes to substituted bicyclo[2.2.1]hept-2-en-7-syn-amines are limited. This paper reports use of (n5-C5H5)Fe-(CO)2(n1-C5H5) (1) as a synthetic equivalent of 5-amino-1,3-cyclopentadiene in cycloaddition reactions. The previously reported cycloadducts of 1 and alkenes were treated with ammonium cerium(IV) nitrate, bromine, or chlorine in acetonitrile containing sodium azide to give the corresponding acyl azides in which the CON3 group replaced the (n5-C5H5)Fe(CO)2 group with retention of stereochemistry in good yield. Thermal Curtius rearrangement of these acyl azides proceeded stereospecifically in excellent yield. This regioselective and stereoselective sequence provides a useful route to substituted 7-syn-amino-2-norbornenes.",

author = "Glass, {Richard S.} and McConnell, {Wesley W.} and Andruski, {Stephen W.}",

year = "1986",

doi = "10.1021/jo00376a012",

language = "English (US)",

volume = "51",

pages = "5123--5127",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

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T1 - (η5-C5H5)Fe(CO)2(η1-C5R5). A Useful Synthetic Equivalent of 5-Amino-1,3-cyclopentadiene in Cycloaddition Reactions

AU - Glass, Richard S.

AU - McConnell, Wesley W.

AU - Andruski, Stephen W.

PY - 1986

Y1 - 1986

N2 - Diels-Alder reactions of 5-amino- 1,3-cyclopentadiene have not been reported, and other stereoselective, high-yield routes to substituted bicyclo[2.2.1]hept-2-en-7-syn-amines are limited. This paper reports use of (n5-C5H5)Fe-(CO)2(n1-C5H5) (1) as a synthetic equivalent of 5-amino-1,3-cyclopentadiene in cycloaddition reactions. The previously reported cycloadducts of 1 and alkenes were treated with ammonium cerium(IV) nitrate, bromine, or chlorine in acetonitrile containing sodium azide to give the corresponding acyl azides in which the CON3 group replaced the (n5-C5H5)Fe(CO)2 group with retention of stereochemistry in good yield. Thermal Curtius rearrangement of these acyl azides proceeded stereospecifically in excellent yield. This regioselective and stereoselective sequence provides a useful route to substituted 7-syn-amino-2-norbornenes.

AB - Diels-Alder reactions of 5-amino- 1,3-cyclopentadiene have not been reported, and other stereoselective, high-yield routes to substituted bicyclo[2.2.1]hept-2-en-7-syn-amines are limited. This paper reports use of (n5-C5H5)Fe-(CO)2(n1-C5H5) (1) as a synthetic equivalent of 5-amino-1,3-cyclopentadiene in cycloaddition reactions. The previously reported cycloadducts of 1 and alkenes were treated with ammonium cerium(IV) nitrate, bromine, or chlorine in acetonitrile containing sodium azide to give the corresponding acyl azides in which the CON3 group replaced the (n5-C5H5)Fe(CO)2 group with retention of stereochemistry in good yield. Thermal Curtius rearrangement of these acyl azides proceeded stereospecifically in excellent yield. This regioselective and stereoselective sequence provides a useful route to substituted 7-syn-amino-2-norbornenes.

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(η⁵-C₅H₅)Fe(CO)₂(η¹-C₅R₅). A Useful Synthetic Equivalent of 5-Amino-1,3-cyclopentadiene in Cycloaddition Reactions

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