α-Bromo-α, α-difluoroallyl derivatives as synthetic intermediate: Nucleophilic substitution of α-bromo-α, α-difluoroallyl derivatives in the presence of palladium catalysts
The palladium catalyzed nucleophilic substitution of alpha-bromo-alpha,alpha-difluoroallyl derivatives turned out to be an efficient method for the preparation of several fluorinated organic molecules. Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP)...
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| Veröffentlicht in: | Chemical & pharmaceutical bulletin 2000, Vol.48 (6), p.885-888 |
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| container_title | Chemical & pharmaceutical bulletin |
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| creator | KIRIHARA, M TAKUWA, T OKUMURA, M WAKIKAWA, T TAKAHATA, H MOMOSE, T TAKEUCHI, Y NEMOTO, H |
| description | The palladium catalyzed nucleophilic substitution of alpha-bromo-alpha,alpha-difluoroallyl derivatives turned out to be an efficient method for the preparation of several fluorinated organic molecules. Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP) to give the 3-substituted 1,1-difluoroalkenes. Phenylzinc chloride and tributylphenyltin afforded 1-fluoro-1,3-diphenylpropene. The radical bromination of 3-substituted 1,1-difluoroalkenes provided 1-substituted BDFPs, and a 1-substituted BDFP reacted with carbon nucleophiles to give 1,3-disubstituted 3,3-difluoroalkenes. For the reaction of nitrogen nucleophiles with BDFP, an amine and the sodium salts of the carbamates reacted with BDFP at the gamma-position. However, the sodium salts of the sulfoneamide predominantly attacked at the alpha-position. |
| doi_str_mv | 10.1248/cpb.48.885 |
| format | Article |
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Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP) to give the 3-substituted 1,1-difluoroalkenes. Phenylzinc chloride and tributylphenyltin afforded 1-fluoro-1,3-diphenylpropene. The radical bromination of 3-substituted 1,1-difluoroalkenes provided 1-substituted BDFPs, and a 1-substituted BDFP reacted with carbon nucleophiles to give 1,3-disubstituted 3,3-difluoroalkenes. For the reaction of nitrogen nucleophiles with BDFP, an amine and the sodium salts of the carbamates reacted with BDFP at the gamma-position. 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Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP) to give the 3-substituted 1,1-difluoroalkenes. Phenylzinc chloride and tributylphenyltin afforded 1-fluoro-1,3-diphenylpropene. The radical bromination of 3-substituted 1,1-difluoroalkenes provided 1-substituted BDFPs, and a 1-substituted BDFP reacted with carbon nucleophiles to give 1,3-disubstituted 3,3-difluoroalkenes. For the reaction of nitrogen nucleophiles with BDFP, an amine and the sodium salts of the carbamates reacted with BDFP at the gamma-position. However, the sodium salts of the sulfoneamide predominantly attacked at the alpha-position.</description><subject>Aliphatic compounds</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Fluorine Compounds - chemistry</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Mass Spectrometry</subject><subject>Organic chemistry</subject><subject>Palladium - chemistry</subject><subject>Preparations and properties</subject><issn>0009-2363</issn><issn>1347-5223</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqNkc1u1TAQhS1ERW8LGx4AeYFYVOTi_yTdQcVPpapsYB059kQ1SuLgcSrdx2ofpM-Er-6VYMlqNJpvzozOIeQ1Z1suVPPBLf1WNdum0c_IhktVV1oI-ZxsGGNtJaSRp-QM8RdjQrNaviCnnDXGcG025PHpofqU4hSrp4f3tDQ-DOMaU7TjuBuphxTubQ73gNQixd2c7yAHR8OcIU3gg81wSW9XN0Jc7sJYRrj2mENec4gzjcNetP-_C2GmRZ4uCRBmB_vlpVDWh3WizmY77jDjS3Iy2BHh1bGek59fPv-4-lbdfP96ffXxpnKa61ypAfp6YLo2PUgvmQPnBtv43tVeWgAPrDijWu-dki3jggvXc2MEt1q51spz8u6gu6T4ewXM3RTQQflnhrhiV3PBtKrbAl4cQJciYoKhW1KYbNp1nHX7hLqSUFdKSajAb46qa1_8-wc9RFKAt0fAorPjkOzsAv7lFDe6MfIPDuWjJw</recordid><startdate>2000</startdate><enddate>2000</enddate><creator>KIRIHARA, M</creator><creator>TAKUWA, T</creator><creator>OKUMURA, M</creator><creator>WAKIKAWA, T</creator><creator>TAKAHATA, H</creator><creator>MOMOSE, T</creator><creator>TAKEUCHI, Y</creator><creator>NEMOTO, H</creator><general>Maruzen</general><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>2000</creationdate><title>α-Bromo-α, α-difluoroallyl derivatives as synthetic intermediate: Nucleophilic substitution of α-bromo-α, α-difluoroallyl derivatives in the presence of palladium catalysts</title><author>KIRIHARA, M ; TAKUWA, T ; OKUMURA, M ; WAKIKAWA, T ; TAKAHATA, H ; MOMOSE, T ; TAKEUCHI, Y ; NEMOTO, H</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c515t-4feb7f0576be3d30ceccfa8dbc7d3aeede036349ddc43901212cb16621a54c9a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><topic>Aliphatic compounds</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Fluorine Compounds - chemistry</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Mass Spectrometry</topic><topic>Organic chemistry</topic><topic>Palladium - chemistry</topic><topic>Preparations and properties</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>KIRIHARA, M</creatorcontrib><creatorcontrib>TAKUWA, T</creatorcontrib><creatorcontrib>OKUMURA, M</creatorcontrib><creatorcontrib>WAKIKAWA, T</creatorcontrib><creatorcontrib>TAKAHATA, H</creatorcontrib><creatorcontrib>MOMOSE, T</creatorcontrib><creatorcontrib>TAKEUCHI, Y</creatorcontrib><creatorcontrib>NEMOTO, H</creatorcontrib><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>Chemical & pharmaceutical bulletin</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>KIRIHARA, M</au><au>TAKUWA, T</au><au>OKUMURA, M</au><au>WAKIKAWA, T</au><au>TAKAHATA, H</au><au>MOMOSE, T</au><au>TAKEUCHI, Y</au><au>NEMOTO, H</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>α-Bromo-α, α-difluoroallyl derivatives as synthetic intermediate: Nucleophilic substitution of α-bromo-α, α-difluoroallyl derivatives in the presence of palladium catalysts</atitle><jtitle>Chemical & pharmaceutical bulletin</jtitle><addtitle>Chem Pharm Bull (Tokyo)</addtitle><date>2000</date><risdate>2000</risdate><volume>48</volume><issue>6</issue><spage>885</spage><epage>888</epage><pages>885-888</pages><issn>0009-2363</issn><eissn>1347-5223</eissn><coden>CPBTAL</coden><abstract>The palladium catalyzed nucleophilic substitution of alpha-bromo-alpha,alpha-difluoroallyl derivatives turned out to be an efficient method for the preparation of several fluorinated organic molecules. Several soft carbon nucleophiles regioselectively reacted with 3-bromo-3,3-difluoropropene (BDFP) to give the 3-substituted 1,1-difluoroalkenes. Phenylzinc chloride and tributylphenyltin afforded 1-fluoro-1,3-diphenylpropene. The radical bromination of 3-substituted 1,1-difluoroalkenes provided 1-substituted BDFPs, and a 1-substituted BDFP reacted with carbon nucleophiles to give 1,3-disubstituted 3,3-difluoroalkenes. For the reaction of nitrogen nucleophiles with BDFP, an amine and the sodium salts of the carbamates reacted with BDFP at the gamma-position. However, the sodium salts of the sulfoneamide predominantly attacked at the alpha-position.</abstract><cop>Tokyo</cop><pub>Maruzen</pub><pmid>10866156</pmid><doi>10.1248/cpb.48.885</doi><tpages>4</tpages><oa>free_for_read</oa></addata></record> |
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| ispartof | Chemical & pharmaceutical bulletin, 2000, Vol.48 (6), p.885-888 |
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| source | J-STAGE Free; MEDLINE; EZB-FREE-00999 freely available EZB journals; Free Full-Text Journals in Chemistry |
| subjects | Aliphatic compounds Catalysis Chemistry Exact sciences and technology Fluorine Compounds - chemistry Magnetic Resonance Spectroscopy Mass Spectrometry Organic chemistry Palladium - chemistry Preparations and properties |
| title | α-Bromo-α, α-difluoroallyl derivatives as synthetic intermediate: Nucleophilic substitution of α-bromo-α, α-difluoroallyl derivatives in the presence of palladium catalysts |
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