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. 2017 Dec 12;9(5):1231-1235.
doi: 10.1039/c7sc04854h. eCollection 2018 Feb 7.

Alkylative kinetic resolution of vicinal diols under phase-transfer conditions: a chiral ammonium borinate catalysis

Martin Pawliczek  1 , Takuya Hashimoto  1 , Keiji Maruoka  1
Affiliations

Alkylative kinetic resolution of vicinal diols under phase-transfer conditions: a chiral ammonium borinate catalysis

Martin Pawliczek et al. Chem Sci. .

Abstract

Herein, we report the first alkylative kinetic resolution of vicinal alcohols realized by cooperative use of a chiral quaternary ammonium salt and an achiral borinic acid. In addition, a catalytic regioselective alkylation of a secondary alcohol in the presence of an unprotected primary one is presented, emphasizing the unique selectivity and potential of this ammonium borinate catalysis.

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Figures

Fig. 1
Fig. 1. Cooperative catalysis for the asymmetric functionalization of vicinal diols.
Scheme 1
Scheme 1. Preparation of catalyst 7. Conditions: (a) [(p-cym)RuCl2]2, Bu3P, 3,5-(iC3F7)2C6H3I, K2CO3, NMP, 110 °C, 78% yield; (b) LiOH aq., THF, reflux; (c) BH3·Me2S, THF, reflux, 86% yield (2 steps); (d) PBr3, THF, rt, 88% yield; (e) NH3 aq., CH3CN, 80 °C, 69% yield.
Fig. 2
Fig. 2. The reaction pathways of the ammonium borinate catalyzed alkylation.
Scheme 2
Scheme 2. (a) Catalyst-controlled, regioselective alkylation of the secondary alcohol of (R)-1a. (b) Desymmetrization of meso-diol 12.
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