Platinum(II)-Catalyzed Allylation of CO and CN Bonds under Hydrogenation Conditions
The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amoun...
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Published in | Advanced synthesis & catalysis Vol. 352; no. 17; pp. 2949 - 2954 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
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Weinheim
WILEY-VCH Verlag
22.11.2010
WILEY‐VCH Verlag Wiley |
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Abstract | The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amount of toxic and sensitive organometallic reagents. The allylplatinum intermediates reacted with CO and CN bonds to produce the corresponding homoallylic alcohol and amine derivatives in good yield. The Pt‐catalyzed allylation of CN bonds is the first example performed under hydrogenation conditions. A reaction mechanism initiated with the hydrometalation of allenes by PtH species is proposed based on deuterium labeling studies. |
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AbstractList | The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amount of toxic and sensitive organometallic reagents. The allylplatinum intermediates reacted with C=O and C=N bonds to produce the corresponding homoallylic alcohol and amine derivatives in good yield. The Pt-catalyzed allylation of C=N bonds is the first example performed under hydrogenation conditions. A reaction mechanism initiated with the hydrometalation of allenes by Pt-H species is proposed based on deuterium labeling studies. The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amount of toxic and sensitive organometallic reagents. The allylplatinum intermediates reacted with CO and CN bonds to produce the corresponding homoallylic alcohol and amine derivatives in good yield. The Pt‐catalyzed allylation of CN bonds is the first example performed under hydrogenation conditions. A reaction mechanism initiated with the hydrometalation of allenes by PtH species is proposed based on deuterium labeling studies. |
Author | Kim, Ji-Hwan Jang, Hye-Young Yun, Hoseop Hong, Jong-Tai Kim, Kyunghee Wang, Xi |
Author_xml | – sequence: 1 givenname: Jong-Tai surname: Hong fullname: Hong, Jong-Tai organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 – sequence: 2 givenname: Xi surname: Wang fullname: Wang, Xi organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 – sequence: 3 givenname: Ji-Hwan surname: Kim fullname: Kim, Ji-Hwan organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 – sequence: 4 givenname: Kyunghee surname: Kim fullname: Kim, Kyunghee organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 – sequence: 5 givenname: Hoseop surname: Yun fullname: Yun, Hoseop organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 – sequence: 6 givenname: Hye-Young surname: Jang fullname: Jang, Hye-Young email: hyjang2@ajou.ac.kr organization: Division of Energy Systems Research, Ajou University, Suwon, 443-749, Korea, Fax: (+82)-31-219-1615; phone: (+82)-31-219-2555 |
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Keywords | METAL REAGENTS REVERSE PRENYLATION HOMOALLYLIC ALCOHOLS ALDEHYDE OXIDATION LEVEL ARYLATIVE CYCLIZATION cyclization hydrogenation REDUCTIVE ALDOL CATALYZED CARBONYL ALLYLATION platinum ALLENYL-ALDEHYDES ARYL IODIDES allylation ALLYLIC TRANSFER-REACTION hydrazones |
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Snippet | The nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and... |
Source | Web of Science |
SourceID | webofscience crossref wiley istex |
SourceType | Enrichment Source Index Database Publisher |
StartPage | 2949 |
SubjectTerms | allylation Chemistry Chemistry, Applied Chemistry, Organic cyclization hydrazones hydrogenation Physical Sciences platinum Science & Technology |
Title | Platinum(II)-Catalyzed Allylation of CO and CN Bonds under Hydrogenation Conditions |
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