Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins
Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo...
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| Veröffentlicht in: | Journal of the American Chemical Society 2007-04, Vol.129 (14), p.4456-4462 |
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| container_title | Journal of the American Chemical Society |
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| creator | Hodgson, David M Chung, Ying Kit Nuzzo, Irene Freixas, Glòria Kulikiewicz, Krystyna K Cleator, Ed Paris, Jean-Marc |
| description | Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn−Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g−7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation. |
| doi_str_mv | 10.1021/ja0672932 |
| format | Article |
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Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn−Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g−7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. 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Am. Chem. Soc</addtitle><description>Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn−Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g−7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.</description><subject>Aldehydes - chemistry</subject><subject>Bridged Bicyclo Compounds - chemistry</subject><subject>Catalysis</subject><subject>Chlorohydrins - chemistry</subject><subject>Cyclopropanes - chemistry</subject><subject>Epoxy Compounds - chemistry</subject><subject>Heptanes - chemistry</subject><subject>Hexanes - chemistry</subject><subject>Isomerism</subject><subject>Molecular Structure</subject><subject>Sesquiterpenes - chemical synthesis</subject><subject>Sesquiterpenes - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0E1LwzAYB_Agis7pwS8gvSh4qCZp-pKjbFM3BsrcPHgJT5uEdbbNTFrYvr0ZG3qRHELIj-flj9AVwfcEU_KwApyklEf0CPVITHEYE5ocox7GmIZplkRn6Ny5lX8ympFTdEbSyB-Oe2g2bloLtalU0VVgg8G2qMzamjU00JamCYwOFo2DtrPQKhnMla3LBqpgtDabUioXQCODwbIy1iy30paNu0AnGiqnLg93Hy2eRvPBSzh9fR4PHqchMJK2IYlTznNNZQJ5zngBlHGWc8Z1zqJcq4SRiFNMsrjQUuuEyixmMuMMM8B-waiPbvd1_bjfnXKtqEtXqKqCRpnOiRRHLObZDt7tYWGNc1ZpsbZlDXYrCBa7AMVvgN5eH4p2ea3knzwk5kG4B6Vr1eb3H-yXSLyIxfztXXxMhng2_JyI2PubvYfCiZXprA_P_dP4B6Q_hnY</recordid><startdate>20070411</startdate><enddate>20070411</enddate><creator>Hodgson, David M</creator><creator>Chung, Ying Kit</creator><creator>Nuzzo, Irene</creator><creator>Freixas, Glòria</creator><creator>Kulikiewicz, Krystyna K</creator><creator>Cleator, Ed</creator><creator>Paris, Jean-Marc</creator><general>American Chemical Society</general><scope>BSCLL</scope><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>20070411</creationdate><title>Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins</title><author>Hodgson, David M ; Chung, Ying Kit ; Nuzzo, Irene ; Freixas, Glòria ; Kulikiewicz, Krystyna K ; Cleator, Ed ; Paris, Jean-Marc</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-15799bf2d6abb49ca2494b949fb43bfe6413920185cfdff62d854d89404a05123</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>Aldehydes - chemistry</topic><topic>Bridged Bicyclo Compounds - chemistry</topic><topic>Catalysis</topic><topic>Chlorohydrins - chemistry</topic><topic>Cyclopropanes - chemistry</topic><topic>Epoxy Compounds - chemistry</topic><topic>Heptanes - chemistry</topic><topic>Hexanes - chemistry</topic><topic>Isomerism</topic><topic>Molecular Structure</topic><topic>Sesquiterpenes - chemical synthesis</topic><topic>Sesquiterpenes - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hodgson, David M</creatorcontrib><creatorcontrib>Chung, Ying Kit</creatorcontrib><creatorcontrib>Nuzzo, Irene</creatorcontrib><creatorcontrib>Freixas, Glòria</creatorcontrib><creatorcontrib>Kulikiewicz, Krystyna K</creatorcontrib><creatorcontrib>Cleator, Ed</creatorcontrib><creatorcontrib>Paris, Jean-Marc</creatorcontrib><collection>Istex</collection><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>Hodgson, David M</au><au>Chung, Ying Kit</au><au>Nuzzo, Irene</au><au>Freixas, Glòria</au><au>Kulikiewicz, Krystyna K</au><au>Cleator, Ed</au><au>Paris, Jean-Marc</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2007-04-11</date><risdate>2007</risdate><volume>129</volume><issue>14</issue><spage>4456</spage><epage>4462</epage><pages>4456-4462</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]hexan-2-ols via Sn−Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g−7.5 kg) synthesis of bicyclo[3.1.0]hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-β-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>17373790</pmid><doi>10.1021/ja0672932</doi><tpages>7</tpages></addata></record> |
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| source | MEDLINE; American Chemical Society Journals |
| subjects | Aldehydes - chemistry Bridged Bicyclo Compounds - chemistry Catalysis Chlorohydrins - chemistry Cyclopropanes - chemistry Epoxy Compounds - chemistry Heptanes - chemistry Hexanes - chemistry Isomerism Molecular Structure Sesquiterpenes - chemical synthesis Sesquiterpenes - chemistry |
| title | Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and Chlorohydrins |
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