Catalytic Asymmetric Epoxidation of α,β-Unsaturated Amides: Efficient Synthesis of β-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation−Pd-Catalyzed Epoxide Opening Process
The catalytic asymmetric epoxidation of α,β-unsaturated amides using Sm−BINOL−Ph3AsO complex was succeeded. Using 5−10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding α,β-epoxy amides in up to 99% yield and in more than 99% ee. Moreover,...
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| Veröffentlicht in: | Journal of the American Chemical Society 2002-12, Vol.124 (49), p.14544-14545 |
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| container_issue | 49 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 124 |
| creator | Nemoto, Tetsuhiro Kakei, Hiroyuki Gnanadesikan, Vijay Tosaki, Shin-ya Ohshima, Takashi Shibasaki, Masakatsu |
| description | The catalytic asymmetric epoxidation of α,β-unsaturated amides using Sm−BINOL−Ph3AsO complex was succeeded. Using 5−10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding α,β-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation−Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of β-aryl α-hydroxy amides, including β-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity. |
| doi_str_mv | 10.1021/ja028454e |
| format | Article |
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Using 5−10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding α,β-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation−Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of β-aryl α-hydroxy amides, including β-aryllactyl-leucine methyl esters. 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Am. Chem. Soc</addtitle><description>The catalytic asymmetric epoxidation of α,β-unsaturated amides using Sm−BINOL−Ph3AsO complex was succeeded. Using 5−10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding α,β-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation−Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of β-aryl α-hydroxy amides, including β-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.</description><subject>Alcohols - chemical synthesis</subject><subject>Alkenes - chemistry</subject><subject>Amides - chemical synthesis</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Epoxy Compounds - chemical synthesis</subject><subject>Epoxy Compounds - chemistry</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Palladium - chemistry</subject><subject>Stereoisomerism</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkcFu0zAcxiMEYt3gwAsgX0BCwuDYSezuVpXCQBON1FY7Wo5jg0viFNuVmp04wpU3YQ8y8Qx7EjwarRckTrb1_32fP_tLkicpepUinL5eC4RZlmfqXjJKc4xgnuLifjJCCGFIWUGOkmPv1_GYYZY-TI5SnBX5OGej5PdUBNH0wUgw8X3bquDidrbpdqYWwXQWdBpc_3p5fQVX1ouwdSKoGkxaUyt_evPtB5hpbaRRNoBFb8Nn5Y3_q7mCE9c3UQvP-tp1u34QgZU39hMQYG4VLLsAlsLWqgX_C3Lz_WdZwz11GSPsRwrMN8reGpauk8r7R8kDLRqvHg_rSbJ6O1tOz-D5_N376eQcCkLHARLBtB5nBWWM6pToCjOmcVUpTWoplES0UONCIJLLlDKKKkwyVBOmKa7qLNPkJHm-99247utW-cBb46VqGmFVt_WcYprFm_IIvtiD0nXeO6X5xplWuJ6niN_Wx-_qi-zTwXRbtao-kENfEXg2AMJL0WgnrDT-wGVkHB9FIgf3nPFB7e7mwn3hBSU058tywT--KRcX-eIDvzj4Cun5uts6G__uHwH_ALYTxk0</recordid><startdate>20021211</startdate><enddate>20021211</enddate><creator>Nemoto, Tetsuhiro</creator><creator>Kakei, Hiroyuki</creator><creator>Gnanadesikan, Vijay</creator><creator>Tosaki, Shin-ya</creator><creator>Ohshima, Takashi</creator><creator>Shibasaki, Masakatsu</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</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>20021211</creationdate><title>Catalytic Asymmetric Epoxidation of α,β-Unsaturated Amides: Efficient Synthesis of β-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation−Pd-Catalyzed Epoxide Opening Process</title><author>Nemoto, Tetsuhiro ; Kakei, Hiroyuki ; Gnanadesikan, Vijay ; Tosaki, Shin-ya ; Ohshima, Takashi ; Shibasaki, Masakatsu</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-3a8ff9467887f13fb288f2bbef3dcaec076e96a035c17870b2340d38f72bd44f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Alcohols - chemical synthesis</topic><topic>Alkenes - chemistry</topic><topic>Amides - chemical synthesis</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Epoxy Compounds - chemical synthesis</topic><topic>Epoxy Compounds - chemistry</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Palladium - chemistry</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Nemoto, Tetsuhiro</creatorcontrib><creatorcontrib>Kakei, Hiroyuki</creatorcontrib><creatorcontrib>Gnanadesikan, Vijay</creatorcontrib><creatorcontrib>Tosaki, Shin-ya</creatorcontrib><creatorcontrib>Ohshima, Takashi</creatorcontrib><creatorcontrib>Shibasaki, Masakatsu</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</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>Nemoto, Tetsuhiro</au><au>Kakei, Hiroyuki</au><au>Gnanadesikan, Vijay</au><au>Tosaki, Shin-ya</au><au>Ohshima, Takashi</au><au>Shibasaki, Masakatsu</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalytic Asymmetric Epoxidation of α,β-Unsaturated Amides: Efficient Synthesis of β-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation−Pd-Catalyzed Epoxide Opening Process</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2002-12-11</date><risdate>2002</risdate><volume>124</volume><issue>49</issue><spage>14544</spage><epage>14545</epage><pages>14544-14545</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The catalytic asymmetric epoxidation of α,β-unsaturated amides using Sm−BINOL−Ph3AsO complex was succeeded. Using 5−10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding α,β-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation−Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of β-aryl α-hydroxy amides, including β-aryllactyl-leucine methyl esters. 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| subjects | Alcohols - chemical synthesis Alkenes - chemistry Amides - chemical synthesis Catalysis Chemistry Epoxy Compounds - chemical synthesis Epoxy Compounds - chemistry Exact sciences and technology Organic chemistry Palladium - chemistry Stereoisomerism |
| title | Catalytic Asymmetric Epoxidation of α,β-Unsaturated Amides: Efficient Synthesis of β-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation−Pd-Catalyzed Epoxide Opening Process |
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