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Volumn 50, Issue 8, 2011, Pages 1877-1881

Identification of a valuable kinetic process in copper-catalyzed asymmetric allylic alkylation

Author keywords

alkylation; allylic compounds; asymmetric catalysis; copper; Grignard reagents

Indexed keywords

ALLYLIC COMPOUNDS; ASYMMETRIC ALLYLIC ALKYLATIONS; ASYMMETRIC CATALYSIS; DYNAMIC KINETIC ASYMMETRIC TRANSFORMATIONS; GRIGNARD REAGENT; KINETIC PROCESS; REACTION CONDITIONS;

EID: 79951806729     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201005373     Document Type: Article
Times cited : (45)

References (67)
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    • Substrate 1 was formed insitu by treatment of (E)-pent-3-en-2-yl acetate with trimethylsilylbromide (1.4equiv) at room temperature for 4h. Control experiments proved that generated TMSOAc was inert under the reaction conditions
    • Substrate 1 was formed insitu by treatment of (E)-pent-3-en-2-yl acetate with trimethylsilylbromide (1.4equiv) at room temperature for 4h. Control experiments proved that generated TMSOAc was inert under the reaction conditions.
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    • (E)-4-chloropent-2-ene (2) has been successfully used in nickel-catalyzed enantioselective dynamic resolution process.
    • (E)-4-chloropent-2-ene (2) has been successfully used in nickel-catalyzed enantioselective dynamic resolution process:, S. Son, G. C. Fu, J. Am. Chem. Soc. 2008, 130, 2756.
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    • Slow addition of the Grignard reagent is known to favor the formation of the organocopper reagent instead of the organocuprate. See Ref.[1e]
    • Slow addition of the Grignard reagent is known to favor the formation of the organocopper reagent instead of the organocuprate. See Ref.[1e].
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    • however, no formation of the Zisomer was detected in the alkylation of allylic phosphonates
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    • 2 represents the difference in energy between the conformers of substrate 2. The value has been calculated with Gaussian 03 using MP2/6- 311G**//PBE 1PBE/6-31 1G** methods. See the Supporting Information for experimental details
    • 2 represents the difference in energy between the conformers of substrate 2. The value has been calculated with Gaussian 03 using MP2/6-311G**//PBE1PBE/6-311G** methods. See the Supporting Information for experimental details.
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    • 1HNMR methods used to determine the proportion of each isomer have an error of about 3 %
    • 1HNMR methods used to determine the proportion of each isomer have an error of about 3 %.
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    • For the unique previous example of transition-metal-catalyzed SKR, see:, L. C. Miller, J. M. Ndungu, R. Sarpong, Angew. Chem. 2009, 121, 2434
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    • III intermediate in the reaction mechanism, see
    • III intermediate in the reaction mechanism, see
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    • N2 adducts
    • N2 adducts.
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    • -1
    • -1.
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    • Ligand L5 is known to be efficient for the alkylation of cinnamyl chloride
    • Ligand L5 is known to be efficient for the alkylation of cinnamyl chloride:, K. Tissot-Croset, D. Polet, A. Alexakis, Angew. Chem. 2004, 116, 2480
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    • For reports on the special reactivity of aryl Grignard reagents in copper-catalyzed allylic substitution, see
    • For reports on the special reactivity of aryl Grignard reagents in copper-catalyzed allylic substitution, see
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    • See Ref.[10g]
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    • (E)-5-chloro-2,6-dimethylhept-3-ene and (E)-5-chloro-2,2,6,6- tetramethylhept-3-ene have been evaluated in the reaction conditions. Unfortunately, an undesired elimination reaction leading to the formation of a diene and a lack of reactivity were respectively observed
    • (E)-5-chloro-2,6-dimethylhept-3-ene and (E)-5-chloro-2,2,6,6- tetramethylhept-3-ene have been evaluated in the reaction conditions. Unfortunately, an undesired elimination reaction leading to the formation of a diene and a lack of reactivity were respectively observed.
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    • For previous examples of copper-catalyzed asymmetric allylic alkylation/cross-metathesis sequences involving an acrylate as a coupling partner, see
    • For previous examples of copper-catalyzed asymmetric allylic alkylation/cross-metathesis sequences involving an acrylate as a coupling partner, see
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    • This SKR/cross-metathesis sequence could be particularly interesting since the copper-catalyzed asymmetric allylic alkylation of crotyl chloride remained a preeminent challenge in this field, affording after extensive optimizations only 80 %ee for the γ-alkylated product
    • This SKR/cross-metathesis sequence could be particularly interesting since the copper-catalyzed asymmetric allylic alkylation of crotyl chloride remained a preeminent challenge in this field, affording after extensive optimizations only 80 %ee for the γ-alkylated product.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.