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Synthesis and Reactivity of 1,2- and 1,3-Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo-DMPE and -DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis
Reactions of enantiopure (S)‐[(η5‐C5H5)Re(NO)(PPh3)(=CH2)]+ PF6– [(S)‐2] and PH2CH2(CH2)nCH2PH2 (0.5 equiv.) give (SReSRe)‐[(η5‐C5H5)Re(NO)(PPh3){CH2PH2CH2(CH2)nCH2PH2CH2}(Ph3P)(ON)Re(η5‐C5H5)]2+ 2PF6– [n = 0/1, (SReSRe)‐3/4; 65–62/77–58 %]. Reaction of racemic 2 (BF4– salt) and PH2(CH2)2PH2 (0.5 eq...
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Published in: | European Journal of Inorganic Chemistry 2005-08, Vol.2005 (15), p.2983-2998 |
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description | Reactions of enantiopure (S)‐[(η5‐C5H5)Re(NO)(PPh3)(=CH2)]+ PF6– [(S)‐2] and PH2CH2(CH2)nCH2PH2 (0.5 equiv.) give (SReSRe)‐[(η5‐C5H5)Re(NO)(PPh3){CH2PH2CH2(CH2)nCH2PH2CH2}(Ph3P)(ON)Re(η5‐C5H5)]2+ 2PF6– [n = 0/1, (SReSRe)‐3/4; 65–62/77–58 %]. Reaction of racemic 2 (BF4– salt) and PH2(CH2)2PH2 (0.5 equiv.) gives the meso and rac diastereomers of 3 (BF4– salts) in 28 % and 38 % yields after crystallization. Treatments of (SReSRe)‐3/4 with tBuOK and then (S)‐2 give the tetrarhenium complexes (SReSReSReSRe)[{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PHCH2(CH2)nCH2PH}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2]2+ 2PF6– [n = 0/1, (SReSReSReSRe)‐7/8; 89–88/98–87 %]. The crystal structure of(SReSReSReSRe)‐7 is determined and its conformation analyzed. Reactions of (SReSReSReSRe)‐7/8 and tBuOK give air‐sensitive diphosphanes (SReSReSReSRe)‐{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PCH2(CH2)nCH2P}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2 [n = 0/1, (SReSReSReSRe)‐9/10; 92/62 %]. Additions of (a) PhIO give the corresponding dioxides (72/62 %), and (b) [Rh(NBD)2]+ PF6– give the corresponding chelates [(P–P)Rh(NBD)]+ PF6– (75/82 %) (NBD = norbornadiene). These catalyze hydrogenations of protected dehydroamino acids and hydrosilylations of propiophenone with only modest enantioselectivities. Similar results are obtained when (SReSReSReSRe)‐9/10 are applied in rhodium‐catalyzed conjugate additions of aryl boronic acids, or palladium‐catalyzed allylic alkylations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) |
doi_str_mv | 10.1002/ejic.200500254 |
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A.</creator><creatorcontrib>Kromm, Klemenz ; Eichenseher, Sandra ; Prommesberger, Markus ; Hampel, Frank ; Gladysz, J. A.</creatorcontrib><description>Reactions of enantiopure (S)‐[(η5‐C5H5)Re(NO)(PPh3)(=CH2)]+ PF6– [(S)‐2] and PH2CH2(CH2)nCH2PH2 (0.5 equiv.) give (SReSRe)‐[(η5‐C5H5)Re(NO)(PPh3){CH2PH2CH2(CH2)nCH2PH2CH2}(Ph3P)(ON)Re(η5‐C5H5)]2+ 2PF6– [n = 0/1, (SReSRe)‐3/4; 65–62/77–58 %]. Reaction of racemic 2 (BF4– salt) and PH2(CH2)2PH2 (0.5 equiv.) gives the meso and rac diastereomers of 3 (BF4– salts) in 28 % and 38 % yields after crystallization. Treatments of (SReSRe)‐3/4 with tBuOK and then (S)‐2 give the tetrarhenium complexes (SReSReSReSRe)[{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PHCH2(CH2)nCH2PH}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2]2+ 2PF6– [n = 0/1, (SReSReSReSRe)‐7/8; 89–88/98–87 %]. The crystal structure of(SReSReSReSRe)‐7 is determined and its conformation analyzed. Reactions of (SReSReSReSRe)‐7/8 and tBuOK give air‐sensitive diphosphanes (SReSReSReSRe)‐{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PCH2(CH2)nCH2P}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2 [n = 0/1, (SReSReSReSRe)‐9/10; 92/62 %]. Additions of (a) PhIO give the corresponding dioxides (72/62 %), and (b) [Rh(NBD)2]+ PF6– give the corresponding chelates [(P–P)Rh(NBD)]+ PF6– (75/82 %) (NBD = norbornadiene). These catalyze hydrogenations of protected dehydroamino acids and hydrosilylations of propiophenone with only modest enantioselectivities. Similar results are obtained when (SReSReSReSRe)‐9/10 are applied in rhodium‐catalyzed conjugate additions of aryl boronic acids, or palladium‐catalyzed allylic alkylations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</description><identifier>ISSN: 1434-1948</identifier><identifier>EISSN: 1099-0682</identifier><identifier>DOI: 10.1002/ejic.200500254</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Chiral diphosphane ; Hydrogenation ; Hydrosilylation ; Phosphane oxide ; Rhenium ; Rhodium</subject><ispartof>European Journal of Inorganic Chemistry, 2005-08, Vol.2005 (15), p.2983-2998</ispartof><rights>Copyright © 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3274-b8639ab5bad54f8377c669bedaa62f0fff88f5fc7131ae12eb64e89836932d933</citedby><cites>FETCH-LOGICAL-c3274-b8639ab5bad54f8377c669bedaa62f0fff88f5fc7131ae12eb64e89836932d933</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>313,314,776,780,788,27901,27903,27904</link.rule.ids></links><search><creatorcontrib>Kromm, Klemenz</creatorcontrib><creatorcontrib>Eichenseher, Sandra</creatorcontrib><creatorcontrib>Prommesberger, Markus</creatorcontrib><creatorcontrib>Hampel, Frank</creatorcontrib><creatorcontrib>Gladysz, J. A.</creatorcontrib><title>Synthesis and Reactivity of 1,2- and 1,3-Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo-DMPE and -DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis</title><title>European Journal of Inorganic Chemistry</title><addtitle>Eur. J. Inorg. Chem</addtitle><description>Reactions of enantiopure (S)‐[(η5‐C5H5)Re(NO)(PPh3)(=CH2)]+ PF6– [(S)‐2] and PH2CH2(CH2)nCH2PH2 (0.5 equiv.) give (SReSRe)‐[(η5‐C5H5)Re(NO)(PPh3){CH2PH2CH2(CH2)nCH2PH2CH2}(Ph3P)(ON)Re(η5‐C5H5)]2+ 2PF6– [n = 0/1, (SReSRe)‐3/4; 65–62/77–58 %]. Reaction of racemic 2 (BF4– salt) and PH2(CH2)2PH2 (0.5 equiv.) gives the meso and rac diastereomers of 3 (BF4– salts) in 28 % and 38 % yields after crystallization. Treatments of (SReSRe)‐3/4 with tBuOK and then (S)‐2 give the tetrarhenium complexes (SReSReSReSRe)[{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PHCH2(CH2)nCH2PH}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2]2+ 2PF6– [n = 0/1, (SReSReSReSRe)‐7/8; 89–88/98–87 %]. The crystal structure of(SReSReSReSRe)‐7 is determined and its conformation analyzed. Reactions of (SReSReSReSRe)‐7/8 and tBuOK give air‐sensitive diphosphanes (SReSReSReSRe)‐{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PCH2(CH2)nCH2P}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2 [n = 0/1, (SReSReSReSRe)‐9/10; 92/62 %]. Additions of (a) PhIO give the corresponding dioxides (72/62 %), and (b) [Rh(NBD)2]+ PF6– give the corresponding chelates [(P–P)Rh(NBD)]+ PF6– (75/82 %) (NBD = norbornadiene). These catalyze hydrogenations of protected dehydroamino acids and hydrosilylations of propiophenone with only modest enantioselectivities. Similar results are obtained when (SReSReSReSRe)‐9/10 are applied in rhodium‐catalyzed conjugate additions of aryl boronic acids, or palladium‐catalyzed allylic alkylations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</description><subject>Chiral diphosphane</subject><subject>Hydrogenation</subject><subject>Hydrosilylation</subject><subject>Phosphane oxide</subject><subject>Rhenium</subject><subject>Rhodium</subject><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNqFkcFS2zAQhj2dMlNKe-15HwAHybJluzdwEqCTApPA9KiR7VUs6sgZSaH1m_ZxqpDC9MZJq53_2_13_ij6QsmEEpKc4aNuJgkhWfhk6bvomJKyjAkvkvehTlka0zItPkQfnXskhDDC-HH0ZzUa36HTDqRpYYmy8fpJ-xEGBfQ0iZ_b9JTFU73tBrftpEEHvpMeqsF4qQ3Mh52FqtNW9rDs0OjdBuZWrjdovPsK57bptMfG74KgH-FmeMIe7tFbuUEfWkM8_X43e160r-5gtcVGv2yRFuHBbG1w1eMaW1jodZA6UIOFmZHG68Fhj3vfCJUME8dwzqfoSMne4ed_70n0MJ_dV1fx4vbyujpfxA1L8jSuC85KWWe1bLNUFSzPG87LGlspeaKIUqooVKaanDIqkSZY8xSLsmC8ZElbMnYSTQ5zGzs4Z1GJYHUj7SgoEftcxD4X8ZpLAMoD8CvcM76hFrNv19X_bHxgtfP4-5WV9qfgOcsz8ePmUlysqny6vODiiv0FwPKkzw</recordid><startdate>200508</startdate><enddate>200508</enddate><creator>Kromm, Klemenz</creator><creator>Eichenseher, Sandra</creator><creator>Prommesberger, Markus</creator><creator>Hampel, Frank</creator><creator>Gladysz, J. A.</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>200508</creationdate><title>Synthesis and Reactivity of 1,2- and 1,3-Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo-DMPE and -DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis</title><author>Kromm, Klemenz ; Eichenseher, Sandra ; Prommesberger, Markus ; Hampel, Frank ; Gladysz, J. A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3274-b8639ab5bad54f8377c669bedaa62f0fff88f5fc7131ae12eb64e89836932d933</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Chiral diphosphane</topic><topic>Hydrogenation</topic><topic>Hydrosilylation</topic><topic>Phosphane oxide</topic><topic>Rhenium</topic><topic>Rhodium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kromm, Klemenz</creatorcontrib><creatorcontrib>Eichenseher, Sandra</creatorcontrib><creatorcontrib>Prommesberger, Markus</creatorcontrib><creatorcontrib>Hampel, Frank</creatorcontrib><creatorcontrib>Gladysz, J. A.</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>European Journal of Inorganic Chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kromm, Klemenz</au><au>Eichenseher, Sandra</au><au>Prommesberger, Markus</au><au>Hampel, Frank</au><au>Gladysz, J. A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Reactivity of 1,2- and 1,3-Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo-DMPE and -DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis</atitle><jtitle>European Journal of Inorganic Chemistry</jtitle><addtitle>Eur. J. Inorg. Chem</addtitle><date>2005-08</date><risdate>2005</risdate><volume>2005</volume><issue>15</issue><spage>2983</spage><epage>2998</epage><pages>2983-2998</pages><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>Reactions of enantiopure (S)‐[(η5‐C5H5)Re(NO)(PPh3)(=CH2)]+ PF6– [(S)‐2] and PH2CH2(CH2)nCH2PH2 (0.5 equiv.) give (SReSRe)‐[(η5‐C5H5)Re(NO)(PPh3){CH2PH2CH2(CH2)nCH2PH2CH2}(Ph3P)(ON)Re(η5‐C5H5)]2+ 2PF6– [n = 0/1, (SReSRe)‐3/4; 65–62/77–58 %]. Reaction of racemic 2 (BF4– salt) and PH2(CH2)2PH2 (0.5 equiv.) gives the meso and rac diastereomers of 3 (BF4– salts) in 28 % and 38 % yields after crystallization. Treatments of (SReSRe)‐3/4 with tBuOK and then (S)‐2 give the tetrarhenium complexes (SReSReSReSRe)[{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PHCH2(CH2)nCH2PH}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2]2+ 2PF6– [n = 0/1, (SReSReSReSRe)‐7/8; 89–88/98–87 %]. The crystal structure of(SReSReSReSRe)‐7 is determined and its conformation analyzed. Reactions of (SReSReSReSRe)‐7/8 and tBuOK give air‐sensitive diphosphanes (SReSReSReSRe)‐{(η5‐C5H5)Re(NO)(PPh3)(CH2)}2{PCH2(CH2)nCH2P}{(CH2)(Ph3P)(ON)Re(η5‐C5H5)}2 [n = 0/1, (SReSReSReSRe)‐9/10; 92/62 %]. Additions of (a) PhIO give the corresponding dioxides (72/62 %), and (b) [Rh(NBD)2]+ PF6– give the corresponding chelates [(P–P)Rh(NBD)]+ PF6– (75/82 %) (NBD = norbornadiene). These catalyze hydrogenations of protected dehydroamino acids and hydrosilylations of propiophenone with only modest enantioselectivities. Similar results are obtained when (SReSReSReSRe)‐9/10 are applied in rhodium‐catalyzed conjugate additions of aryl boronic acids, or palladium‐catalyzed allylic alkylations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/ejic.200500254</doi><tpages>16</tpages></addata></record> |
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subjects | Chiral diphosphane Hydrogenation Hydrosilylation Phosphane oxide Rhenium Rhodium |
title | Synthesis and Reactivity of 1,2- and 1,3-Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo-DMPE and -DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis |
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