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. 2018 May 16;9(23):5191-5196.
doi: 10.1039/c8sc01486h. eCollection 2018 Jun 21.

Facile synthesis of α-aminoboronic acids from amines and potassium acyltrifluoroborates (KATs) via trifluoroborate-iminiums (TIMs)

Tomoya Shiro  1 , Anne Schuhmacher  1 , Moritz K Jackl  1 , Jeffrey W Bode  1
Affiliations

Facile synthesis of α-aminoboronic acids from amines and potassium acyltrifluoroborates (KATs) via trifluoroborate-iminiums (TIMs)

Tomoya Shiro et al. Chem Sci. .

Abstract

We report the facile formation of trifluoroborate-iminiums (TIMs) from potassium acyltrifluoroborates (KATs) and the transformation of TIMs to α-aminotrifluoroborates by reduction or Grignard additions. Conditions for the hydrolysis of α-aminotrifluoroborates to α-aminoboronic acids, which are important biologically active compounds, were established. This new methodology allows access to sterically demanding α-aminoboronic acids that are not easily prepared with currently available methods. This work also introduces TIMs, that can be easily prepared and handled, as a new category of functional groups that serve as precursors to valuable organic compounds.

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Figures

Fig. 1
Fig. 1. Overview of the chemistry of TIMs including formation from KATs and transformation to α-aminotrifluoroborates and α-aminoboronic acids.
Scheme 1
Scheme 1. Substrate scope for the formation of TIMs from KATs and amines. aDMF used instead of CH3CN.
Scheme 2
Scheme 2. Substrate scope for the reduction of TIMs yielding monosubstituted α-aminotrifluoroborates.
Scheme 3
Scheme 3. Substrate scope for the addition of Grignard reagents to TIMs yielding fully substituted α-aminotrifluoroborates.
Scheme 4
Scheme 4. Substrate scope for the protodeborylation of fully substituted α-aminotrifluoroborates using Zr(OiPr)4.
Scheme 5
Scheme 5. Substrate scope for the formation of α-aminoboronic acids from α-aminotrifluoroborates using SiCl4. Compound 58 and 62 were isolated as TFA salts after purification by preparative HPLC.
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