Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes
A regio‐ and diastereoselective copper‐catalyzed carbomagnesiation of 1,2‐dialkylated cyclopropenes is reported. The regioselectivity is controlled by a subtle tethered Lewis basic moiety. The chelating moieties allow the differentiation between two electronically tantamount organometallic intermedi...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2021-12, Vol.60 (50), p.26368-26372 |
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| creator | Cohen, Yair Marek, Ilan |
| description | A regio‐ and diastereoselective copper‐catalyzed carbomagnesiation of 1,2‐dialkylated cyclopropenes is reported. The regioselectivity is controlled by a subtle tethered Lewis basic moiety. The chelating moieties allow the differentiation between two electronically tantamount organometallic intermediates. Further functionalization grants access to polysubstituted stereodefined cyclopropanes bearing up to five alkyl groups.
The copper‐catalyzed carbomagnesiation reaction of cyclopropenes is a well‐established method for the synthesis of stereodefined cyclopropanes. All existing reports to date proceeded towards the formation of the electronically more stable organometallic intermediate. Herein we report a regioselective addition to 1,2‐dialkyl‐substituted cyclopropene possessing a tethered directing group to direct the organometallic species towards the formation of single regioisomer intermediate out of two electronically unbiased possibilities. |
| doi_str_mv | 10.1002/anie.202111382 |
| format | Article |
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The copper‐catalyzed carbomagnesiation reaction of cyclopropenes is a well‐established method for the synthesis of stereodefined cyclopropanes. All existing reports to date proceeded towards the formation of the electronically more stable organometallic intermediate. Herein we report a regioselective addition to 1,2‐dialkyl‐substituted cyclopropene possessing a tethered directing group to direct the organometallic species towards the formation of single regioisomer intermediate out of two electronically unbiased possibilities.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202111382</identifier><identifier>PMID: 34617656</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>carbon quaternary stereocenters ; Chelation ; copper-catalyzed carbomagnesiation ; Cyclopropane ; directing group ; Intermediates ; Organic compounds ; Regioselectivity ; Stereoselectivity</subject><ispartof>Angewandte Chemie International Edition, 2021-12, Vol.60 (50), p.26368-26372</ispartof><rights>2021 Wiley‐VCH GmbH</rights><rights>2021 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3732-de8375599cf88d4f0aa786f3cb23d430c674bda9e168490dbe897a2471a98e8b3</citedby><cites>FETCH-LOGICAL-c3732-de8375599cf88d4f0aa786f3cb23d430c674bda9e168490dbe897a2471a98e8b3</cites><orcidid>0000-0001-9154-2320</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202111382$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202111382$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34617656$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Cohen, Yair</creatorcontrib><creatorcontrib>Marek, Ilan</creatorcontrib><title>Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A regio‐ and diastereoselective copper‐catalyzed carbomagnesiation of 1,2‐dialkylated cyclopropenes is reported. The regioselectivity is controlled by a subtle tethered Lewis basic moiety. The chelating moieties allow the differentiation between two electronically tantamount organometallic intermediates. Further functionalization grants access to polysubstituted stereodefined cyclopropanes bearing up to five alkyl groups.
The copper‐catalyzed carbomagnesiation reaction of cyclopropenes is a well‐established method for the synthesis of stereodefined cyclopropanes. All existing reports to date proceeded towards the formation of the electronically more stable organometallic intermediate. Herein we report a regioselective addition to 1,2‐dialkyl‐substituted cyclopropene possessing a tethered directing group to direct the organometallic species towards the formation of single regioisomer intermediate out of two electronically unbiased possibilities.</description><subject>carbon quaternary stereocenters</subject><subject>Chelation</subject><subject>copper-catalyzed carbomagnesiation</subject><subject>Cyclopropane</subject><subject>directing group</subject><subject>Intermediates</subject><subject>Organic compounds</subject><subject>Regioselectivity</subject><subject>Stereoselectivity</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqFkM9Kw0AQhxdRbK1ePUrBiwdT90-S3T2WtGqhKKg9L5tkIlvTbM0mSm8-gs_ok7iltYIXTzMD3_xm-BA6JXhAMKZXujIwoJgSQpige6hLIkoCxjnb933IWMBFRDroyLm554XA8SHqsDAmPI7iLpqNTA1ZA3n_AZ6NdVD6ybxBP9F1ahfQ6LLUjbFV3xZ9ckm_Pj5HRpcvq9J3j23qGtO06_VklZV2WdslVOCO0UGhSwcn29pDs-vxU3IbTO9vJslwGmSMMxrkIBiPIimzQog8LLDWXMQFy1LK8pDhLOZhmmsJJBahxHkKQnJNQ060FCBS1kMXm1x_-LUF16iFcRn4lyuwrVM0EhgTGWHp0fM_6Ny2deW_UzTGTMpobauHBhsqq61zNRRqWZuFrleKYLUWrtbC1U64XzjbxrbpAvId_mPYA3IDvJsSVv_EqeHdZPwb_g0NrY5L</recordid><startdate>20211206</startdate><enddate>20211206</enddate><creator>Cohen, Yair</creator><creator>Marek, Ilan</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-9154-2320</orcidid></search><sort><creationdate>20211206</creationdate><title>Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes</title><author>Cohen, Yair ; Marek, Ilan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3732-de8375599cf88d4f0aa786f3cb23d430c674bda9e168490dbe897a2471a98e8b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>carbon quaternary stereocenters</topic><topic>Chelation</topic><topic>copper-catalyzed carbomagnesiation</topic><topic>Cyclopropane</topic><topic>directing group</topic><topic>Intermediates</topic><topic>Organic compounds</topic><topic>Regioselectivity</topic><topic>Stereoselectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cohen, Yair</creatorcontrib><creatorcontrib>Marek, Ilan</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cohen, Yair</au><au>Marek, Ilan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2021-12-06</date><risdate>2021</risdate><volume>60</volume><issue>50</issue><spage>26368</spage><epage>26372</epage><pages>26368-26372</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A regio‐ and diastereoselective copper‐catalyzed carbomagnesiation of 1,2‐dialkylated cyclopropenes is reported. The regioselectivity is controlled by a subtle tethered Lewis basic moiety. The chelating moieties allow the differentiation between two electronically tantamount organometallic intermediates. Further functionalization grants access to polysubstituted stereodefined cyclopropanes bearing up to five alkyl groups.
The copper‐catalyzed carbomagnesiation reaction of cyclopropenes is a well‐established method for the synthesis of stereodefined cyclopropanes. All existing reports to date proceeded towards the formation of the electronically more stable organometallic intermediate. Herein we report a regioselective addition to 1,2‐dialkyl‐substituted cyclopropene possessing a tethered directing group to direct the organometallic species towards the formation of single regioisomer intermediate out of two electronically unbiased possibilities.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>34617656</pmid><doi>10.1002/anie.202111382</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-9154-2320</orcidid></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | carbon quaternary stereocenters Chelation copper-catalyzed carbomagnesiation Cyclopropane directing group Intermediates Organic compounds Regioselectivity Stereoselectivity |
| title | Directed Regioselective Carbometallation of 1,2‐Dialkyl‐Substituted Cyclopropenes |
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