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Volumn 53, Issue 43, 2014, Pages 11605-11610

The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines

Author keywords

allyltrifluoroborates; asymmetric catalysis; imines; isomerization; rhodium

Indexed keywords

CATALYSIS; ENANTIOSELECTIVITY; ISOMERIZATION; ISOMERS; NITROGEN COMPOUNDS; OLEFINS; POTASSIUM; RHODIUM;

EID: 84908065765     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201407233     Document Type: Article
Times cited : (96)

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    • The stereochemistries of products 5 b, 5 e, 11 a, 12 c, and 12 d were confirmed by X-ray crystallography. See the Supporting Information for details. The stereochemistries of the remaining products were assigned by analogy. CCDC 1013875 (5 b), 1013876 (5 e), 1013877 (12 c), 1013878 (12 d), and 1019074 (11 a) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
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    • Other cyclic imines 18, 20, and 21 were not suitable substrates in these reactions. Imine 18 reacted with prenyltrifluoroborate 2 a under the conditions shown in Table 1 to provide what appeared to be 19 in only ≈4 % conversion, with the remaining mass balance being unreacted 18. Imines 20 and 21 were completely unreactive.
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    • Attempted reactions of 2 f with imine 4 a led to no traces of any allylation products.
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    • Diene ent- L1 (see Scheme 1a) gave a 71:29 mixture of ent- 5 a and ent- 6 a, and ent- 5 a was formed in 98 % ee. However, the conversion of this reaction was only 65 %. Diene L3 (Ref. [18]) gave a 36:64 mixture of ent- 5 a and ent- 6 a in 85 % conversion (ee values not determined).
    • Diene ent- L1 (see Scheme 1a) gave a 71:29 mixture of ent- 5 a and ent- 6 a, and ent- 5 a was formed in 98 % ee. However, the conversion of this reaction was only 65 %. Diene L3 (Ref. [18]) gave a 36:64 mixture of ent- 5 a and ent- 6 a in 85 % conversion (ee values not determined).
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    • The absolute configurations of the products in Scheme 6 were assigned by analogy with the stereochemical outcomes obtained in previous studies (see Ref. [2]).
    • The absolute configurations of the products in Scheme 6 were assigned by analogy with the stereochemical outcomes obtained in previous studies (see Ref. [2]).
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    • The enyl (σ+π) character of the allylrhodium(I) species could also be invoked in our reactions described herein. For evidence of the enyl (σ+π) character of the allylrhodium(III) species, see.
    • The enyl (σ+π) character of the allylrhodium(I) species could also be invoked in our reactions described herein. For evidence of the enyl (σ+π) character of the allylrhodium(III) species, see:, P. A. Evans, J. D. Nelson, J. Am. Chem. Soc. 1998, 120, 5581-5582.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.