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Volumn 53, Issue 17, 2014, Pages 4382-4385

Short stereoselective synthesis of the phytophthora universal mating hormone α1 using lithiation/borylation reactions

Author keywords

asymmetric synthesis; boron; lithium; natural products; total synthesis

Indexed keywords

BORON; LITHIUM; MOLECULES; STEREOCHEMISTRY;

EID: 84899446404     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201400714     Document Type: Article
Times cited : (20)

References (31)
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    • For syntheses where all stereocenters were controlled, see
    • For syntheses where all stereocenters were controlled, see
  • 9
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    • references?[4] and [6]. For other syntheses where one or more stereocenters was not controlled, see
    • S.-Y. Wang, P. Song, L.-Y. Chan, T.-P. Loh, Org. Lett. 2010, 12, 5166; and references?[4] and [6]. For other syntheses where one or more stereocenters was not controlled, see
    • (2010) Org. Lett. , vol.12 , pp. 5166
    • Wang, S.-Y.1    Song, P.2    Chan, L.-Y.3    Loh, T.-P.4
  • 14
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    • 2O at -78 C within 5?h. Secondary allylic carbamates generally undergo complete lithiation within a few minutes under the same reaction conditions. For lithiation/borylation of alkyl carbamates, see
    • 2O at -78 C within 5?h. Secondary allylic carbamates generally undergo complete lithiation within a few minutes under the same reaction conditions. For lithiation/borylation of alkyl carbamates, see
  • 16
    • 35048834773 scopus 로고    scopus 로고
    • For lithiation/borylation of secondary allylic carbamates, see
    • Angew. Chem. Int. Ed. 2007, 46, 7491; For lithiation/borylation of secondary allylic carbamates, see
    • (2007) Angew. Chem. Int. Ed. , vol.46 , pp. 7491
  • 22
    • 84899440333 scopus 로고    scopus 로고
    • 3 reduction step) was unsuccessful and gave a mixture of products.
    • 3 reduction step) was unsuccessful and gave a mixture of products.
  • 24
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    • These results suggest that coordination of sBuLi to the carbonyl group of the primary alkyl carbamate is reversible, thus allowing for complete lithiation at the α-oxygen allylic site. Reversibility in pre-lithiation complexes of alkyl carbamates has been noted by others. See.
    • These results suggest that coordination of sBuLi to the carbonyl group of the primary alkyl carbamate is reversible, thus allowing for complete lithiation at the α-oxygen allylic site. Reversibility in pre-lithiation complexes of alkyl carbamates has been noted by others. See:, M. J. McGrath, P. O'Brien, Synthesis 2006, 13, 2233.
    • (2006) Synthesis , vol.13 , pp. 2233
    • McGrath, M.J.1    O'Brien, P.2
  • 25
    • 84899414075 scopus 로고    scopus 로고
    • 2/C hydrogenations have been reported
    • 2/C hydrogenations have been reported
  • 28
    • 84899408174 scopus 로고    scopus 로고
    • 2 or Pt avoided epimerization: see Refs.?[15a] and [15b].
    • 2 or Pt avoided epimerization: see Refs.?[15a] and [15b].
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    • 84899420188 scopus 로고    scopus 로고
    • TES protection of the tertiary alcohol in 15 was important for high yields. Attempted double lithiation of the free tertiary alcohol (15 minus TES) with excess sBuLi under the optimized reaction conditions (Table?1, entry?4) gave 15 % of the intended stannane and 60 % of the recovered starting material.
    • TES protection of the tertiary alcohol in 15 was important for high yields. Attempted double lithiation of the free tertiary alcohol (15 minus TES) with excess sBuLi under the optimized reaction conditions (Table?1, entry?4) gave 15 % of the intended stannane and 60 % of the recovered starting material.
  • 30
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    • We considered the use of hindered achiral diamines such as N,N-di-n-butyl bispidine as it has similar reactivity to (-)-sparteine with regard to lithiation efficiency. See:, However, N,N-di-n-butyl bispidine is not as available as (-)-sparteine.
    • We considered the use of hindered achiral diamines such as N,N-di-n-butyl bispidine as it has similar reactivity to (-)-sparteine with regard to lithiation efficiency. See:, M. J. McGrath, J. L. Bilke, P. O'Brien, Chem. Commun. 2006, 2607. However, N,N-di-n-butyl bispidine is not as available as (-)-sparteine.
    • (2006) Chem. Commun. , pp. 2607
    • McGrath, M.J.1    Bilke, J.L.2    O'Brien, P.3
  • 31
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    • Previous stereoselective syntheses range from 17-21 steps and 2-7 % overall yield.
    • Previous stereoselective syntheses range from 17-21 steps and 2-7 % overall yield.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.