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. 2012 Dec 28;48(100):12180-2.
doi: 10.1039/c2cc36199j.

γ-Selective directed catalytic asymmetric hydroboration of 1,1-disubstituted alkenes

Sean M Smith  1 , Gia L Hoang, Rhitankar Pal, Mohammad O Bani Khaled, Liberty S W Pelter, Xiao Cheng Zeng, James M Takacs
Affiliations

γ-Selective directed catalytic asymmetric hydroboration of 1,1-disubstituted alkenes

Sean M Smith et al. Chem Commun (Camb). .

Abstract

Directed catalytic asymmetric hydroborations of 1,1-disubstituted alkenes afford γ-dioxaborato amides and esters in high enantiomeric purity (90-95% ee).

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Figures

Figure 1
Figure 1
Regio- and enantioselective carbonyl-directed CAHB of 1,2- and 1,1-disubstituted alkenes (ee determined after oxidation).
Figure 2
Figure 2
Preparation of chiral γ-hydroxy amides and esters and β-substituted γ-lactones via CAHB-oxidation.
Figure 3
Figure 3
Relative energies of model octahedral intermediates leading to γ- and β-borylation for 1,1- and (E) 1,2-disubstituted substrates (A/B and C/D, respectively; only the vinyl C-H and Rh-H included for clarity.
Scheme 1
Scheme 1
(a) 2% Rh(nbd)2BF4, 4.1% (R,R)-6, 2 equiv tmdBH, THF, 40 °C (74%, 90% ee). (b) KHF2, MeCN/H2O (76%). (c) 5% Pd(OAc)2, 10% RuPhos, K2CO3, PhMe/H2O, 85 °C, 24 h (91%). (d) NaBO3, THF/H2O (98%). (e) 5% Pd(OAc)2, 10% RuPhos, K3PO4, PhMe, 85 °C, 24 h (75%).
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