Direct Suzuki–Miyaura Coupling with Naphthalene-1,8-diaminato (dan)-Substituted Organoborons

Abstract

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.

Fluorinated Aryl Boronates as Building Blocks in Organic Synthesis

“…In 2020, Saito et al [130] . and Tsuchimoto et al [131] . reported a method to apply aryl‐Bdan compounds in Suzuki‐Miyaura cross‐coupling reactions.…”

Pairing Suzuki–Miyaura cross-coupling and catalyst transfer polymerization

“…For the most part, these have only been used as protecting groups, though recent work has shown some of these derivatives can participate in coupling directly. 97,98 The trifluoroborate salts 99 (BF 3 K) have not yet been explored for chain-growth polymerizations, but these derivatives are typically compatible with environmentally friendly solvents such as water and alcohol. Pairing trifluoroborates with water-soluble conjugated polymers 100 could be an exciting new strategy to build polyaromatics in environmentally benign media.…”

Synthetic Chemistry with Lewis Acidity‐Diminished B(aam) and B(dan) Groups: Borylation Reactions and Direct Cross‐Couplings

“…Much more robust C( sp 2 )–B(dan) bonds of aryl– and alkenyl–B(dan)s, which are actually unreactive under the above alkynyl–B(dan)’s conditions, were recently demonstrated to undergo direct SMC by Yoshida–Tsuchimoto [44] (Scheme 53) and Mutoh–Saito [39,45] (Scheme 54) independently. The use of t ‐BuOK as a base under anhydrous conditions is the key to the smooth coupling, and the direct SMC allowed various 2‐pyridyl–B(dan)s to be efficiently transformable into the respective products.…”