Catalytic Asymmetric Reduction of Prochiral Ketones with Chiral β-Amino Alcohol N-Boranes and the Corresponding Tris(oxazaborolidine)borazines

Afroditi Pinaka; Dimitra Dimotikali; Bezhan Chankvetadze; Kyriakos Papadopoulos; Georgios C. Vougioukalakis

doi:10.1055/s-0033-1339943

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(18): 2401-2406
DOI: 10.1055/s-0033-1339943

letter

Catalytic Asymmetric Reduction of Prochiral Ketones with Chiral β-Amino Alcohol N-Boranes and the Corresponding Tris(oxazaborolidine)borazines

Afroditi Pinaka

^aDivision of Physical Chemistry, NCSR Demokritos, 15310 Athens, Greece eMail: kyriakos@chem.demokritos.gr

^bDepartment of Chemical Engineering, NTU Athens, 15780 Athens, Greece

,

Dimitra Dimotikali

^bDepartment of Chemical Engineering, NTU Athens, 15780 Athens, Greece

,

Bezhan Chankvetadze

^cInstitute of Physical and Analytical Chemistry, School of Exact and Natural Sciences,Tbilisi State University, 0170 Tbilisi, Georgia

,

Kyriakos Papadopoulos*

^aDivision of Physical Chemistry, NCSR Demokritos, 15310 Athens, Greece eMail: kyriakos@chem.demokritos.gr

,

Georgios C. Vougioukalakis*

^aDivision of Physical Chemistry, NCSR Demokritos, 15310 Athens, Greece eMail: kyriakos@chem.demokritos.gr

^dDepartment of Chemistry, University of Athens, 15771 Athens, Greece Fax: +30(210)6511766 eMail: vougiouk@chem.uoa.gr

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Abstract

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Dedicated to Professor Nikos Hadjichristidis on the occasion of his 70^th birthday

Abstract

Chiral β-amino alcohol-derived N-borane catalysts, namely noncyclic (2S)- and (2R)-2-amino-2-phenylethanol N-borane and their corresponding cyclic trimeric borazine derivatives, were synthesized and their catalytic activities in the asymmetric reduction of prochiral ketones were examined. Both the noncyclic and cyclic catalysts successfully catalyzed this reaction, giving the desired secondary alcohols in up to 82% isolated yield and with up to 80% enantioselectivity. The noncyclic catalyst was stable in aqueous and organic solvents, whereas the polycyclic borazine was stable only in nonprotic dry organic solvents.

Key words

reductions - catalysis - asymmetric catalysis - asymmetric synthesis - boron - ketones

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Referenzen

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14 Asymmetric Reduction of Acetophenone with Catalyst 1; Typical Procedure A 100 mL, flame-dried, two-necked, round-bottomed flask equipped with a magnetic stirrer bar, was charged with catalyst 1 (0.4 mmol) and anhyd THF (4 mL). BH₃·THF (2.4 mmol, 1.2 equiv) was added under argon from a syringe. A soln of PhCOMe (2 mmol, 0.22 mL) in anhyd THF (2 mL) was added dropwise at 1 mL/h and the solution was then stirred at r.t. under argon for 18 h. When the reaction was complete, the mixture was hydrolyzed by the addition of MeOH (5 mL) and 1 M aq HCl (5 mL) and stirred for 30 min. The mixture was then extracted with Et₂O (3 × 50 mL), and the combined organic extracts were dried (MgSO₄) and concentrated under reduced pressure. The residual crude product was purified by column chromatography [silica gel, EtOAc–hexanes (1:3)] to give enantiomerically enriched 1-phenylethanol as a colorless oil; yield: 0.17 g (70%).
15 Asymmetric Reduction of Acetophenone with Catalyst 2; Typical Procedure A 100 mL, flame-dried, two-necked, round-bottomed flask equipped with a magnetic stirrer bar was charged with catalyst 2 (0.66 mmol) and anhyd THF (4 mL). PhCOMe (2 mmol, 0.22 mL) was then added under argon from a syringe. Subsequently, BH₃·THF (2.4 mmol, 1.2 equiv) was added dropwise with the aid of a syringe pump at a rate of 1 mL/h, and the solution was then stirred at r.t. under argon for 18 h. When the reaction was complete, the mixture was hydrolyzed by addition of MeOH (5 mL) and 1 M aq HCl (5 mL). Workup as described in ref. 14 gave enantiomerically enriched 1-phenylethanol as a colorless oil; yield: 0.19 g (78%).
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