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Volumn 5, Issue 6, 2013, Pages 1239-1247

Diastereodivergent Processes in Palladium-Catalyzed Allylic Alkylation

Author keywords

Alkylation; Asymmetric catalysis; Deracemization; Diastereodivergence; Pi allyl isomerization; Reaction mechanisms

Indexed keywords

ASYMMETRIC ALLYLIC ALKYLATIONS; ASYMMETRIC CATALYSIS; DE-RACEMIZATION; DIASTEREODIVERGENCE; ENANTIOPURE PRODUCTS; PALLADIUM-CATALYZED; REACTION CONDITIONS; REACTION MECHANISM;

EID: 84878502378     PISSN: 18673880     EISSN: 18673899     Source Type: Journal    
DOI: 10.1002/cctc.201200644     Document Type: Article
Times cited : (18)

References (71)
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    • (2010) Catalytic Asymmetric Synthesis
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    • An exception to this definition are the so called enantioconvergent processes, in which both enantiomers of the substrate originate the same enantiomer of the product, through different mechanistic pathways. For more details, see also ref. 4b and 4d.
    • An exception to this definition are the so called enantioconvergent processes, in which both enantiomers of the substrate originate the same enantiomer of the product, through different mechanistic pathways. For more details, see also ref. 4b and 4d.
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    • For the sake of clarity, in this article, the stereochemistry of the molecules (starting materials and products) will be referred to as cis/trans; whilst for the organopalladium intermediates (π-allyl complexes) the syn/anti nomenclature will be employed.
    • For the sake of clarity, in this article, the stereochemistry of the molecules (starting materials and products) will be referred to as cis/trans; whilst for the organopalladium intermediates (π-allyl complexes) the syn/anti nomenclature will be employed.
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    • The nature of the ligand bound to the incoming zero-valent palladium was also found to affect the oxidative addition in a critical way, see ref.16b.
    • The nature of the ligand bound to the incoming zero-valent palladium was also found to affect the oxidative addition in a critical way, see ref.16b.
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    • For other paper related see: J. Xu, X.L. Qiu, F.L. Qing, Beilstein J. Org. Chem. 2008, 4, DOI:.
    • For other paper related see: J. Xu, X.L. Qiu, F.L. Qing, Beilstein J. Org. Chem. 2008, 4, DOI:.
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    • The cis/trans ratio of isomerization was found to be time dependent: 2.3:1 (30min); 1:1.3 (1hour) 1:2 (2h). After prolonged heating, the isomerization was biased by the formation of a by-product (the corresponding conjugate diene, product of elimination).
    • The cis/trans ratio of isomerization was found to be time dependent: 2.3:1 (30min); 1:1.3 (1hour) 1:2 (2h). After prolonged heating, the isomerization was biased by the formation of a by-product (the corresponding conjugate diene, product of elimination).
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    • For selected exemples of diastereodivergent asymmetric transformations outside allylic alkylation, see:
    • For selected exemples of diastereodivergent asymmetric transformations outside allylic alkylation, see:
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    • for seminal work on palladium catalyzed TMM cycloaddition by the Trost group, see:
    • B. M. Trost, N. Cramer, S. M. Silverman, J. Am. Chem. Soc. 2007, 129, 12396-12397; for seminal work on palladium catalyzed TMM cycloaddition by the Trost group, see:
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 12396-12397
    • Trost, B.M.1    Cramer, N.2    Silverman, S.M.3
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    • In this first report, Ito and co-workers observed only moderate enantiomeric excess and diastereomeric ratio;
    • A. Yamamoto, Y. Ito, T. Hayashi, Tetrahedron Lett. 1989, 30, 375-378. In this first report, Ito and co-workers observed only moderate enantiomeric excess and diastereomeric ratio;
    • (1989) Tetrahedron Lett. , vol.30 , pp. 375-378
    • Yamamoto, A.1    Ito, Y.2    Hayashi, T.3
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    • Since the substrate is cis-configured, the use of a stabilized carbanion in palladium catalysis should lead only to the enantioenriched product of similar relative stereochemistry (retention).
    • Since the substrate is cis-configured, the use of a stabilized carbanion in palladium catalysis should lead only to the enantioenriched product of similar relative stereochemistry (retention).
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    • A mechanism involving a ligand-dependant syn oxidative addition seems to be very difficult to rationalize in such a complex system, although it cannot be excluded.
    • A mechanism involving a ligand-dependant syn oxidative addition seems to be very difficult to rationalize in such a complex system, although it cannot be excluded.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.