Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes
The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective...
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| Veröffentlicht in: | Tetrahedron 2019-08, Vol.75 (31), p.4086-4098 |
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| container_title | Tetrahedron |
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| creator | Gilbert, Bradley B. Eey, Stanley T.-C. Ryabchuk, Pavel Garry, Olivia Denmark, Scott E. |
| description | The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.
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| doi_str_mv | 10.1016/j.tet.2019.05.054 |
| format | Article |
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[Display omitted]</description><subject>chemical reactions</subject><subject>chemical structure</subject><subject>Electrophilic selenium</subject><subject>Enantioselective dichlorination</subject><subject>enantioselectivity</subject><subject>Lewis acids</subject><subject>Lewis bases</subject><subject>Redox catalysis</subject><issn>0040-4020</issn><issn>1464-5416</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkVFrFDEUhYNY7Lb6A3yRffRl1ptMJskgCFJsFQr1QZ_D3eROm3U2qcnMwvrrTbu16IuFC3k43z2cm8PYaw4rDly926wmmlYCeL-Cro58xhZcKtl0kqvnbAEgoZEg4JidlLIBAM5F-4Idt1wrA1ov2NerfI0xFRophnnbOJxw3P8iv6SIcQr3ipvCjpZlHxsf3M2YcohYpbhMw3KO64Cl8jj-oEjlJTsacCz06uE9Zd_PP307-9xcXl18Oft42Thp5NR0WgpvvEOUslsPJNB4U1Mp2Xll-nXb9YjknPcO_OC5A-F6oBpa9VJ3rj1lHw6-t_N6S95RnDKO9jaHLea9TRjsv0oMN_Y67awyWmnZV4O3DwY5_ZypTHYbiqNxxEhpLla03GjRV_xpVGhu2la3vKL8gLqcSsk0PCbiYO9KsxtbS7N3pVno6si68-bvUx43_rRUgfcHgOqH7gJlW1yg6MiHXMuxPoX_2P8GE_GqwA</recordid><startdate>20190802</startdate><enddate>20190802</enddate><creator>Gilbert, Bradley B.</creator><creator>Eey, Stanley T.-C.</creator><creator>Ryabchuk, Pavel</creator><creator>Garry, Olivia</creator><creator>Denmark, Scott E.</creator><general>Elsevier Ltd</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7S9</scope><scope>L.6</scope><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20190802</creationdate><title>Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes</title><author>Gilbert, Bradley B. ; Eey, Stanley T.-C. ; Ryabchuk, Pavel ; Garry, Olivia ; Denmark, Scott E.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c484t-5742d8dcaa445bfe2a8d8176645d689b359aaeccddc0dfd1c02c90e80769475c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>chemical reactions</topic><topic>chemical structure</topic><topic>Electrophilic selenium</topic><topic>Enantioselective dichlorination</topic><topic>enantioselectivity</topic><topic>Lewis acids</topic><topic>Lewis bases</topic><topic>Redox catalysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gilbert, Bradley B.</creatorcontrib><creatorcontrib>Eey, Stanley T.-C.</creatorcontrib><creatorcontrib>Ryabchuk, Pavel</creatorcontrib><creatorcontrib>Garry, Olivia</creatorcontrib><creatorcontrib>Denmark, Scott E.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Tetrahedron</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gilbert, Bradley B.</au><au>Eey, Stanley T.-C.</au><au>Ryabchuk, Pavel</au><au>Garry, Olivia</au><au>Denmark, Scott E.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes</atitle><jtitle>Tetrahedron</jtitle><addtitle>Tetrahedron</addtitle><date>2019-08-02</date><risdate>2019</risdate><volume>75</volume><issue>31</issue><spage>4086</spage><epage>4098</epage><pages>4086-4098</pages><issn>0040-4020</issn><eissn>1464-5416</eissn><abstract>The enantioselective dichlorination of alkenes is a continuing challenge in organic synthesis owing to the limitations of selective and independent antarafacial delivery of both electrophilic chlorenium and nucleophilic chloride to an olefin. Development of a general method for the enantioselective dichlorination of isolated alkenes would allow access to a wide variety of polyhalogenated natural products. Accordingly, the enantioselective suprafacial dichlorination of alkenes catalyzed by electrophilic organoselenium reagents has been developed to address these limitations. The evaluation of twenty-three diselenides as precatalysts for enantioselective dichlorination is described, with a maximum e.r. of 76:24 Additionally, mechanistic studies suggest an unexpected Dynamic Kinetic Asymmetric Transformation (DyKAT) process may be operative.
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| ispartof | Tetrahedron, 2019-08, Vol.75 (31), p.4086-4098 |
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| language | eng |
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| source | Elsevier ScienceDirect Journals |
| subjects | chemical reactions chemical structure Electrophilic selenium Enantioselective dichlorination enantioselectivity Lewis acids Lewis bases Redox catalysis |
| title | Organoselenium-catalyzed enantioselective syn-dichlorination of unbiased alkenes |
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