The actually direct Suzuki−Miyaura coupling with "protected" R−B(dan) (dan = naphthalene-1,8-diaminato) was demonstrated to smoothly occur without in situ deprotection of the B(dan) moiety. The use of t-BuOK (Ba(OH) 2 in some cases) as a base under anhydrous conditions is the key to the successful cross-coupling, where R−B(dan) is readily converted into a transmetalation-active borate-form, regardless of the well-accepted diminished boron-Lewis acidity.

This review describes recent advances in the synthesis of anthranilamide/1,8‐diaminonaphthalene‐substituted organoboron compounds with diminished boron Lewis acidity via catalytic B(aam)‐ and B(dan)‐installing borylation reactions, which have attracted growing attention especially in the last five years owing to their unique reactivity, regioselectivity, and the outstanding stability toward air and moisture of organoboron compounds obtained therefrom. Direct Suzuki–Miyaura cross‐couplings with R–B(aam)/B(dan), which were believed to be wholly unreactive until recently, are also discussed.

Copper-catalyzed reaction of organic halides with an unsymmetrical diboron, (pin)B–B(dan), which leads to the direct formation of masked organoboron compounds, is reported.

Pd-Catalyzed cross-coupling and Rh-catalyzed 1,4-addition with Ar-B(aam) become feasible without the need for prior acidic deprotection

H–B(dan) serves as a B(dan) electrophile to give directly R–B(dan) by the reaction with Grignard reagents under transition metal-free conditions.

An unsymmetrical diboron bearing an anthranilamide (aam) substituent was synthesized and was found to be coupled with aryl halides through the palladium-catalyzed Miyaura-Ishiyama-type reaction. The selective transfer of aam-substituted boryl moiety led to exclusive formation of diverse Ar-B(aam).

Trialkylsilyllithium species have turned out to be facilely generated by treating hexaalkyldisilanes with methyllithium in the presence of tris(N,N-tetramethylene)phosphoric triamide (TPPA) as an activator, which can be trapped by boron electrophiles to afford silylboronic esters including long-awaited Me3Si–B(pin).

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