A Practical Synthetic Approach to Chiral (α-Chloroalkyl)boronic Esters via Iridium-Catalyzed Chemoselective Hydrogenation of Chloro-Substituted Alkenyl Boronates

Stephen J. Roseblade; Eva Casas-Arcé; Ulrike Nettekoven; Ivana Gazić Smilović; Antonio Zanotti-Gerosa; Zdenko Časar

doi:10.1055/s-0033-1338512

Synthesis, Table of Contents

Synthesis 2013; 45(20): 2824-2831
DOI: 10.1055/s-0033-1338512

practical synthetic procedures

A Practical Synthetic Approach to Chiral (α-Chloroalkyl)boronic Esters via Iridium-Catalyzed Chemoselective Hydrogenation of Chloro-Substituted Alkenyl Boronates

Stephen J. Roseblade

^aJohnson Matthey, Catalysis and Chiral Technologies, Unit 28, Cambridge Science Park, Milton Road, Cambridge CB4 0FP, UK

,

Eva Casas-Arcé

^aJohnson Matthey, Catalysis and Chiral Technologies, Unit 28, Cambridge Science Park, Milton Road, Cambridge CB4 0FP, UK

,

Ulrike Nettekoven

^bSolvias AG, Business Unit Synthesis and Catalysis, Römerpark 2, 4303 Kaiseraugst, Switzerland

,

Ivana Gazić Smilović

^cLek Pharmaceuticals, d.d., Sandoz Development Center Slovenia, API Development, Organic Synthesis Department, Kolodvorska 27, 1234 Mengeš, Slovenia

,

Antonio Zanotti-Gerosa

^aJohnson Matthey, Catalysis and Chiral Technologies, Unit 28, Cambridge Science Park, Milton Road, Cambridge CB4 0FP, UK

,

Zdenko Časar*

^cLek Pharmaceuticals, d.d., Sandoz Development Center Slovenia, API Development, Organic Synthesis Department, Kolodvorska 27, 1234 Mengeš, Slovenia

^dSandoz GmbH, Global Portfolio Management API, 6250 Kundl, Austria Fax: +43(5338)200418 Email: zdenko.casar@sandoz.com

^eFaculty of Pharmacy, University of Ljubljana, 1000 Ljubljana, Slovenia

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Abstract

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Dedicated to Prof. Dr. Dominique Lorcy (University of Rennes 1, France) on the occasion of her birthday

Abstract

Chiral (α-chloroalkyl)boronic esters are obtained by homogeneous asymmetric iridium-catalyzed chemoselective hydrogenation of (1-chloro-1-alkenyl)boronic esters. P,N–Iridium catalysis provides low level of dehalogenation during the hydrogenation, while the catalyst activity and enantioselectivity essentially depends on the applied P,N ligand features. Fine tuning of P,N ligand structures enables high conversions, broad substrate acceptance, and high to excellent enantioselectivities with enantiomeric excess values up to 94% along with low levels of dechlorination. Low catalyst loading with S/C = 200 can also be achieved for the preparation of an industrially important isobutyl derivative.

Key words

alkenes - alkyl halides - asymmetric synthesis - chemoselectivity - hydrogenation

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References

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