Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles
Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium...
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Veröffentlicht in: | Journal of the American Chemical Society 2017-11, Vol.139 (43), p.15324-15327 |
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creator | García-Ruiz, Cristina Chen, Jack L.-Y Sandford, Christopher Feeney, Kathryn Lorenzo, Paula Berionni, Guillaume Mayr, Herbert Aggarwal, Varinder K |
description | Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser’s salt, Togni’s reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. The allylboronate complexes were determined to be 7 to 10 orders of magnitude more reactive than the parent boronic ester. |
doi_str_mv | 10.1021/jacs.7b10240 |
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By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser’s salt, Togni’s reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. 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Am. Chem. Soc</addtitle><description>Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser’s salt, Togni’s reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. The allylboronate complexes were determined to be 7 to 10 orders of magnitude more reactive than the parent boronic ester.</description><subject>Communication</subject><subject>esters</subject><subject>fluorine</subject><subject>imines</subject><subject>Lewis acids</subject><subject>Lewis bases</subject><subject>moieties</subject><subject>protocols</subject><subject>pyridines</subject><issn>0002-7863</issn><issn>1520-5126</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqFkcFvFCEUh0mjsWv11rOZo4dO5cHADj002WxaNWliovVMGOaNy4YdpjDTWv96WXetbdLE03vAx-9BPkKOgZ4CZfBhbWw6nTe5r-gBmYFgtBTA5Asyo5Sycl5Lfkhep7TOy4rV8IocMkVZzRnMCH4bMWJIA1rXOVssvL_3uV5OvR1d6I13v8y2OSuuV1h8RfNnOxWh27FNiJkasViGzeDxJ6bizo2r4sKjHWMYVs5jekNedsYnfLuvR-T75cX18lN59eXj5-XiqjSVoGNpRNtUikvZMtYBKmAdV5xzabpOtrWxxgpTz42sma0aVK2p7FwohAZaRmvgR-R8lztMzQZbi_0YjddDdBsT73UwTj896d1K_wi3WuRIoVQOeL8PiOFmwjTqjUsWvTc9hilpBiAV46Dkf1FQAiqomKozerJDbQwpReweXgRUbyXqrUS9l5jxd49_8QD_tfZv9PbWOkwxa0rPZ_0Gn7yoMQ</recordid><startdate>20171101</startdate><enddate>20171101</enddate><creator>García-Ruiz, Cristina</creator><creator>Chen, Jack L.-Y</creator><creator>Sandford, Christopher</creator><creator>Feeney, Kathryn</creator><creator>Lorenzo, Paula</creator><creator>Berionni, Guillaume</creator><creator>Mayr, Herbert</creator><creator>Aggarwal, Varinder K</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-0768-5199</orcidid><orcidid>https://orcid.org/0000-0003-0344-6430</orcidid><orcidid>https://orcid.org/0000-0002-4015-0674</orcidid><orcidid>https://orcid.org/0000-0002-5422-9113</orcidid></search><sort><creationdate>20171101</creationdate><title>Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles</title><author>García-Ruiz, Cristina ; Chen, Jack L.-Y ; Sandford, Christopher ; Feeney, Kathryn ; Lorenzo, Paula ; Berionni, Guillaume ; Mayr, Herbert ; Aggarwal, Varinder K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a450t-a5db49366d22f1e912f393336aff6d8acac5a87a682c4be9da4c759e1b1d20813</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Communication</topic><topic>esters</topic><topic>fluorine</topic><topic>imines</topic><topic>Lewis acids</topic><topic>Lewis bases</topic><topic>moieties</topic><topic>protocols</topic><topic>pyridines</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>García-Ruiz, Cristina</creatorcontrib><creatorcontrib>Chen, Jack L.-Y</creatorcontrib><creatorcontrib>Sandford, Christopher</creatorcontrib><creatorcontrib>Feeney, Kathryn</creatorcontrib><creatorcontrib>Lorenzo, Paula</creatorcontrib><creatorcontrib>Berionni, Guillaume</creatorcontrib><creatorcontrib>Mayr, Herbert</creatorcontrib><creatorcontrib>Aggarwal, Varinder K</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>García-Ruiz, Cristina</au><au>Chen, Jack L.-Y</au><au>Sandford, Christopher</au><au>Feeney, Kathryn</au><au>Lorenzo, Paula</au><au>Berionni, Guillaume</au><au>Mayr, Herbert</au><au>Aggarwal, Varinder K</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2017-11-01</date><risdate>2017</risdate><volume>139</volume><issue>43</issue><spage>15324</spage><epage>15327</epage><pages>15324-15327</pages><issn>0002-7863</issn><issn>1520-5126</issn><eissn>1520-5126</eissn><abstract>Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser’s salt, Togni’s reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. 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subjects | Communication esters fluorine imines Lewis acids Lewis bases moieties protocols pyridines |
title | Stereospecific Allylic Functionalization: The Reactions of Allylboronate Complexes with Electrophiles |
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