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. 2019 Jan 22;24(3):377.
doi: 10.3390/molecules24030377.

Direct Transformation From Arylamines to Aryl Naphthalene-1,8-diamino Boronamides: A Metal-Free Sandmeyer-Type Process

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Free PMC article

Direct Transformation From Arylamines to Aryl Naphthalene-1,8-diamino Boronamides: A Metal-Free Sandmeyer-Type Process

Siyi Ding et al. Molecules. .
Free PMC article

Abstract

A direct metal-free transformation from arylamines to aryl naphthalene-1,8-diamino boronamides, a type of masked boronic acid, has been developed based on Sandmeyer-type reactions. A nonsymmetrical diboron reagent, B(pin)-B(dan), was utilized as the borylating reagent, and the B(dan) moiety was transferred to the aim products selectively. This conversion tolerated a series of functional groups, including chloro, bromo, fluoro, ester, hydroxy, cyano and amide.

Keywords: boronamides; metal-free borylation; sandmeyer-type reaction.

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Different routes to synthesize aryl B(dan) derivatives.
Scheme 2
Scheme 2
Different routes to synthesize aryl B(dan) derivatives. (a) Unless otherwise noted, the reaction conditions are as follows: aryl amine (0.2 mmol, 2.0 eq.), B(pin)-B(dan) (0.1 mmol, 1.0 eq.), t-BuONO (0.2 mmol, 2.0 eq.), TBAI (0.01 mmol, 0.1 eq.), NaOAc (0.15 mmol, 1.5 eq.), BPO (0.01 mmol, 0.1 eq.), MeCN (0.6 mL), 80 °C. (b) Yield of isolated product. (c) Large scale experiments, reaction conditions: aryl amine (2 mmol, 2.0 eq.), B(pin)-B(dan) (1 mmol, 1.0 eq.), t-BuONO (2 mmol, 2.0 eq.), TBAI (0.1 mmol, 0.1 eq.), NaOAc (1.5 mmol, 1.5 eq.), BPO (0.1 mmol, 0.1 eq.), MeCN (6.0 mL), 80 °C.
Scheme 3
Scheme 3
Successive and selective Suzuki-Miyaura cross-coupling reaction using 3-bromophenyl B(dan) 2j as the starting material.

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