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Volumn 55, Issue 15, 2016, Pages 4701-4706

Lewis Acid Catalyzed Borotropic Shifts in the Design of Diastereo- and Enantioselective γ-Additions of Allylboron Moieties to Aldimines

Author keywords

boron; borotropic shift; diastereoselective synthesis; enantioselective catalysis; homoallylic amines

Indexed keywords

BORON; CATALYSIS; STEREOSELECTIVITY;

EID: 84960158762     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201600546     Document Type: Article
Times cited : (52)

References (76)
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    • For catalytic diastereo- and enantioselective additions of allyl units to different types of aldimines, see
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    • For representative diastereoselective additions of allyl fragments with enantiomerically pure reagents and/or aldimines, see
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    • See the Supporting Information for details
    • See the Supporting Information for details.
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    • Allylzinc reagents are likely not involved because such highly nucleophilic entities would not survive the reaction conditions, demonstrated previously to be acidic (see Ref. [2a])
    • Allylzinc reagents are likely not involved because such highly nucleophilic entities would not survive the reaction conditions, demonstrated previously to be acidic (see Ref. [2a]).
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    • Catalyst screening indicated that aminophenol 1 b generally delivers somewhat higher enantioselectivity than 1 a
    • Catalyst screening indicated that aminophenol 1 b generally delivers somewhat higher enantioselectivity than 1 a.
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    • Initial isomerization of rac- 8 to (E)- and (Z)- 3 (prior to the first γ-addition to generate the chiral allylboron iii) is unlikely, as in that case, anti- 4 a would be formed with high diastereoselectivity. The stronger propensity of an aminophenol-based allylboron reagent to undergo a 1,3-borotropic shift is almost certainly due to its more Lewis acidic boron atom
    • Initial isomerization of rac- 8 to (E)- and (Z)- 3 (prior to the first γ-addition to generate the chiral allylboron iii) is unlikely, as in that case, anti- 4 a would be formed with high diastereoselectivity. The stronger propensity of an aminophenol-based allylboron reagent to undergo a 1,3-borotropic shift is almost certainly due to its more Lewis acidic boron atom.
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    • Attempts to observe (Z)- i through NMR spectroscopy were unsuccessful, as only a minute fraction of the aminophenol present is converted into the active catalyst
    • Attempts to observe (Z)- i through NMR spectroscopy were unsuccessful, as only a minute fraction of the aminophenol present is converted into the active catalyst.
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    • The chloro-substituted allylboron reagent was prepared by catalytic Z-selective cross-metathesis; see
    • The chloro-substituted allylboron reagent was prepared by catalytic Z-selective cross-metathesis; see: M. J. Koh, T. T. Nguyen, H. Zhang, R. R. Schrock, A. H. Hoveyda, Nature 2016, DOI: 10.1038/nature17396.
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    • Koh, M.J.1    Nguyen, T.T.2    Zhang, H.3    Schrock, R.R.4    Hoveyda, A.H.5


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.