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84899436683
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For syntheses where all stereocenters were controlled, see
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For syntheses where all stereocenters were controlled, see
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8
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S. R. Harutyunyan, Z. Zhao, T. d. Hartog, K. Bouwmeester, A. J. Minnaard, B. L. Feringa, F. Govers, Proc. Natl. Acad. Sci. USA 2008, 105, 8507
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78449298713
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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
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84899433148
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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
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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
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84899440333
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3 reduction step) was unsuccessful and gave a mixture of products.
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3 reduction step) was unsuccessful and gave a mixture of products.
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23
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33746040068
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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.
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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:, M. J. McGrath, P. O'Brien, Synthesis 2006, 13, 2233.
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84899414075
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2/C hydrogenations have been reported
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2/C hydrogenations have been reported
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26
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29344444314
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T. Nakai, A. Yajima, K. Akasaka, T. Kaihoko, M. Ohtaki, T. Nukuda, H. Ohrui, G. Yabuta, Biosci. Biotechnol. Biochem. 2005, 69, 2401
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84878049285
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J. Buter, E. A.-H. Yeh, O. W. Budavich, K. Damodaran, A. J. Minnaard, D. P. Curran, J. Org. Chem. 2013, 78, 4913
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28
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84899408174
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2 or Pt avoided epimerization: see Refs.?[15a] and [15b].
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2 or Pt avoided epimerization: see Refs.?[15a] and [15b].
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29
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84899420188
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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.
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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.
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33745224132
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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.
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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:, 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.
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(2006)
Chem. Commun.
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McGrath, M.J.1
Bilke, J.L.2
O'Brien, P.3
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31
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84899464664
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Previous stereoselective syntheses range from 17-21 steps and 2-7 % overall yield.
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Previous stereoselective syntheses range from 17-21 steps and 2-7 % overall yield.
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