Platinum(II)-Catalyzed Allylation of CO and CN 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 inAdvanced synthesis & catalysis Vol. 352; no. 17; pp. 2949 - 2954
Main Authors Hong, Jong-Tai, Wang, Xi, Kim, Ji-Hwan, Kim, Kyunghee, Yun, Hoseop, Jang, Hye-Young
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 22.11.2010
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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 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.
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 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.
Author Kim, Ji-Hwan
Jang, Hye-Young
Yun, Hoseop
Hong, Jong-Tai
Kim, Kyunghee
Wang, Xi
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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...
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wiley
istex
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StartPage 2949
SubjectTerms allylation
Chemistry
Chemistry, Applied
Chemistry, Organic
cyclization
hydrazones
hydrogenation
Physical Sciences
platinum
Science & Technology
Title Platinum(II)-Catalyzed Allylation of CO and CN Bonds under Hydrogenation Conditions
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