A Direct, Concise, and Enantioselective Synthesis of 2-Substituted 4,4,4-Trifluorobutane-1,3-diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde
A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes was examined. A catalytic amount (30 mol %) of commercially availabl...
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| Veröffentlicht in: | Chemistry, an Asian journal an Asian journal, 2015-12, Vol.10 (12), p.2701-2707 |
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| container_title | Chemistry, an Asian journal |
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| creator | Funabiki, Kazumasa Furuno, Yudai Yano, Yosuke Sakaida, Yuta Kubota, Yasuhiro Matsui, Masaki |
| description | A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes was examined. A catalytic amount (30 mol %) of commercially available and inexpensive l‐prolinamide is quite effective as an organocatalyst for the catalytic in situ generation of gaseous and unstable trifluoroacetaldehyde from its hemiacetal, and a successive asymmetric direct aldol reaction with various aldehydes in dichloromethane at 0 °C, followed by reduction with sodium borohydride, gives 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols in moderate to good yields (31–84 %) with low diastereoselectivities and good to excellent enantioselectivities (64–97 % ee).
Being picky: A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes is described (see scheme). |
| doi_str_mv | 10.1002/asia.201500607 |
| format | Article |
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Being picky: A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes is described (see scheme).</description><identifier>ISSN: 1861-4728</identifier><identifier>EISSN: 1861-471X</identifier><identifier>DOI: 10.1002/asia.201500607</identifier><identifier>PMID: 26206587</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Acetaldehyde - analogs & derivatives ; Acetaldehyde - chemistry ; Aldehydes - chemistry ; aldol reaction ; asymmetric synthesis ; Borohydrides - chemistry ; Butylene Glycols - chemical synthesis ; Butylene Glycols - chemistry ; Catalysis ; Chemistry ; fluorine ; Ketones - chemistry ; Methylene Chloride - chemistry ; organocatalysis ; Oxidation-Reduction ; Proline - analogs & derivatives ; Proline - chemistry ; Stereoisomerism ; synthesis design</subject><ispartof>Chemistry, an Asian journal, 2015-12, Vol.10 (12), p.2701-2707</ispartof><rights>2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5187-e8f93ebcb4242416a43dda247aa2db3435ef3f3d159ab09e141cd1315540576a3</citedby><cites>FETCH-LOGICAL-c5187-e8f93ebcb4242416a43dda247aa2db3435ef3f3d159ab09e141cd1315540576a3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fasia.201500607$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fasia.201500607$$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/26206587$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Funabiki, Kazumasa</creatorcontrib><creatorcontrib>Furuno, Yudai</creatorcontrib><creatorcontrib>Yano, Yosuke</creatorcontrib><creatorcontrib>Sakaida, Yuta</creatorcontrib><creatorcontrib>Kubota, Yasuhiro</creatorcontrib><creatorcontrib>Matsui, Masaki</creatorcontrib><title>A Direct, Concise, and Enantioselective Synthesis of 2-Substituted 4,4,4-Trifluorobutane-1,3-diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde</title><title>Chemistry, an Asian journal</title><addtitle>Chem. Asian J</addtitle><description>A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes was examined. A catalytic amount (30 mol %) of commercially available and inexpensive l‐prolinamide is quite effective as an organocatalyst for the catalytic in situ generation of gaseous and unstable trifluoroacetaldehyde from its hemiacetal, and a successive asymmetric direct aldol reaction with various aldehydes in dichloromethane at 0 °C, followed by reduction with sodium borohydride, gives 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols in moderate to good yields (31–84 %) with low diastereoselectivities and good to excellent enantioselectivities (64–97 % ee).
Being picky: A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes is described (see scheme).</description><subject>Acetaldehyde - analogs & derivatives</subject><subject>Acetaldehyde - chemistry</subject><subject>Aldehydes - chemistry</subject><subject>aldol reaction</subject><subject>asymmetric synthesis</subject><subject>Borohydrides - chemistry</subject><subject>Butylene Glycols - chemical synthesis</subject><subject>Butylene Glycols - chemistry</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>fluorine</subject><subject>Ketones - chemistry</subject><subject>Methylene Chloride - chemistry</subject><subject>organocatalysis</subject><subject>Oxidation-Reduction</subject><subject>Proline - analogs & derivatives</subject><subject>Proline - chemistry</subject><subject>Stereoisomerism</subject><subject>synthesis design</subject><issn>1861-4728</issn><issn>1861-471X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkU1v1DAQhiMEoqVw5YgsceGwWfwRJ9njsi3LiooithW9WZN4Ql2ydrEdIP-LH4hXWyLEBc3BlvzMM7bfLHvO6JxRyl9DMDDnlElKS1o9yI5ZXbK8qNj1w2nP66PsSQi3lEpOF_Xj7IiXnJayro6zX0tyajy2cUZWzrYm4IyA1eTMgo3GBezTmfmOZDvaeIPBBOI6wvPt0IRo4hBRk2KWKr_0pusH510zRLCYs5nItXF9IG8gJMpZkgTkwn8B61qI0I_RtGRjyTZ5yBotekgj7X7AlQ0Rmh7JZIUWU4vGm1Hj0-xRB33AZ_frSXb19uxy9S4_v1hvVsvzvJWsrnKsu4XApm0KnoqVUAitgRcVANeNKITETnRCM7mAhi6QFazVTDApCyqrEsRJ9urgvfPu24Ahqp0JLfZ9ep8bgmJVSeuacyoT-vIf9NYN3qbbJUpWLH03Z4maH6jWuxA8durOmx34UTGq9nmqfZ5qyjM1vLjXDs0O9YT_CTABiwPww_Q4_kenltvN8m95fug1IeLPqRf8V1VWopLq84e1qten15_WH9-rWvwGeRO8rQ</recordid><startdate>201512</startdate><enddate>201512</enddate><creator>Funabiki, Kazumasa</creator><creator>Furuno, Yudai</creator><creator>Yano, Yosuke</creator><creator>Sakaida, Yuta</creator><creator>Kubota, Yasuhiro</creator><creator>Matsui, Masaki</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</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>K9.</scope><scope>7X8</scope></search><sort><creationdate>201512</creationdate><title>A Direct, Concise, and Enantioselective Synthesis of 2-Substituted 4,4,4-Trifluorobutane-1,3-diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde</title><author>Funabiki, Kazumasa ; Furuno, Yudai ; Yano, Yosuke ; Sakaida, Yuta ; Kubota, Yasuhiro ; Matsui, Masaki</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5187-e8f93ebcb4242416a43dda247aa2db3435ef3f3d159ab09e141cd1315540576a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Acetaldehyde - analogs & derivatives</topic><topic>Acetaldehyde - chemistry</topic><topic>Aldehydes - chemistry</topic><topic>aldol reaction</topic><topic>asymmetric synthesis</topic><topic>Borohydrides - chemistry</topic><topic>Butylene Glycols - chemical synthesis</topic><topic>Butylene Glycols - chemistry</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>fluorine</topic><topic>Ketones - chemistry</topic><topic>Methylene Chloride - chemistry</topic><topic>organocatalysis</topic><topic>Oxidation-Reduction</topic><topic>Proline - analogs & derivatives</topic><topic>Proline - chemistry</topic><topic>Stereoisomerism</topic><topic>synthesis design</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Funabiki, Kazumasa</creatorcontrib><creatorcontrib>Furuno, Yudai</creatorcontrib><creatorcontrib>Yano, Yosuke</creatorcontrib><creatorcontrib>Sakaida, Yuta</creatorcontrib><creatorcontrib>Kubota, Yasuhiro</creatorcontrib><creatorcontrib>Matsui, Masaki</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>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry, an Asian journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Funabiki, Kazumasa</au><au>Furuno, Yudai</au><au>Yano, Yosuke</au><au>Sakaida, Yuta</au><au>Kubota, Yasuhiro</au><au>Matsui, Masaki</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Direct, Concise, and Enantioselective Synthesis of 2-Substituted 4,4,4-Trifluorobutane-1,3-diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde</atitle><jtitle>Chemistry, an Asian journal</jtitle><addtitle>Chem. Asian J</addtitle><date>2015-12</date><risdate>2015</risdate><volume>10</volume><issue>12</issue><spage>2701</spage><epage>2707</epage><pages>2701-2707</pages><issn>1861-4728</issn><eissn>1861-471X</eissn><abstract>A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes was examined. A catalytic amount (30 mol %) of commercially available and inexpensive l‐prolinamide is quite effective as an organocatalyst for the catalytic in situ generation of gaseous and unstable trifluoroacetaldehyde from its hemiacetal, and a successive asymmetric direct aldol reaction with various aldehydes in dichloromethane at 0 °C, followed by reduction with sodium borohydride, gives 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols in moderate to good yields (31–84 %) with low diastereoselectivities and good to excellent enantioselectivities (64–97 % ee).
Being picky: A direct, concise, and enantioselective synthesis of 2‐substituted 4,4,4‐trifluorobutane‐1,3‐diols based on the organocatalytic asymmetric direct aldol reaction of an ethyl hemiacetal of trifluoroacetaldehyde with various aldehydes is described (see scheme).</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>26206587</pmid><doi>10.1002/asia.201500607</doi><tpages>7</tpages></addata></record> |
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| ispartof | Chemistry, an Asian journal, 2015-12, Vol.10 (12), p.2701-2707 |
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| subjects | Acetaldehyde - analogs & derivatives Acetaldehyde - chemistry Aldehydes - chemistry aldol reaction asymmetric synthesis Borohydrides - chemistry Butylene Glycols - chemical synthesis Butylene Glycols - chemistry Catalysis Chemistry fluorine Ketones - chemistry Methylene Chloride - chemistry organocatalysis Oxidation-Reduction Proline - analogs & derivatives Proline - chemistry Stereoisomerism synthesis design |
| title | A Direct, Concise, and Enantioselective Synthesis of 2-Substituted 4,4,4-Trifluorobutane-1,3-diols Based on the Organocatalytic In Situ Generation of Unstable Trifluoroacetaldehyde |
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