Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines

We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generatio...

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Veröffentlicht in:	Journal of the American Chemical Society 2011-08, Vol.133 (33), p.12956-12959
Hauptverfasser:	Soheili, Arash, Tambar, Uttam K
Format:	Artikel
Sprache:	eng
Schlagworte:	Allyl Compounds - chemistry Amination Amines - chemistry Catalysis Organic Chemistry Phenomena Palladium - chemistry
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creator	Soheili, Arash Tambar, Uttam K
description	We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.
doi_str_mv	10.1021/ja204717b
format	Article
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Am. Chem. Soc</addtitle><description>We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.</description><subject>Allyl Compounds - chemistry</subject><subject>Amination</subject><subject>Amines - chemistry</subject><subject>Catalysis</subject><subject>Organic Chemistry Phenomena</subject><subject>Palladium - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkE1Lw0AQhhdRbK0e_AOSi4hgdD-7m2MpfkFB0PYkEia7E0nJR91NhP57U1t78vQy8MzDzEvIOaO3jHJ2twROpWY6OyBDpjiNFePjQzKklPJYm7EYkJMQlv0ouWHHZMCZToSiyZAs5lA7rKIptFCu28JGk7Jcl5usihraoqmjnoje-Y34iN9a_MY6RK8I3kP9iRXWbdTk0Rx9W4Bf_25hOCVHOZQBz3Y5IouH-_n0KZ69PD5PJ7MYhKFtLJXKReYQbKJ5gs4pC05I1FIoxiQYaR3wXBhljVVaQaZppo3JlLWOZyhG5GrrXfnmq8PQplURLJYl1Nh0ITVGcs0Z4z15vSWtb0LwmKcrX1T9xSmj6abEdF9iz17srF1WoduTf631wOUWABvSZdP5un_yH9EPbqp4Vg</recordid><startdate>20110824</startdate><enddate>20110824</enddate><creator>Soheili, Arash</creator><creator>Tambar, Uttam K</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20110824</creationdate><title>Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines</title><author>Soheili, Arash ; Tambar, Uttam K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a380t-455f3bdeac9729edd5cad34e7435114a84cda2f385c8c575ab70b788b5ccd2be3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Allyl Compounds - chemistry</topic><topic>Amination</topic><topic>Amines - chemistry</topic><topic>Catalysis</topic><topic>Organic Chemistry Phenomena</topic><topic>Palladium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Soheili, Arash</creatorcontrib><creatorcontrib>Tambar, Uttam K</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Soheili, Arash</au><au>Tambar, Uttam K</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2011-08-24</date><risdate>2011</risdate><volume>133</volume><issue>33</issue><spage>12956</spage><epage>12959</epage><pages>12956-12959</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. 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subjects	Allyl Compounds - chemistry Amination Amines - chemistry Catalysis Organic Chemistry Phenomena Palladium - chemistry
title	Tandem Catalytic Allylic Amination and [2,3]-Stevens Rearrangement of Tertiary Amines
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