Stereospecific palladium-catalyzed borylation reaction of 1-alkenyl halides with diispropylaminoborane

Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies

“…Several transition-metal-catalyzed methods have been developed during the course of the past two decades for the borylation of aryl and alkenyl halides, 4 , 5 C(sp 2 )–H borylation 6 and the hydroboration of alkynes, 7 and all of these methods show a broad functional group compatibility. However, the application of these methods to the preparation of pharmaceuticals has been limited by the costs associated with the use of expensive transition-metal catalysts and the potential for contamination of the product with residual transition-metal impurities.…”

Borylation of Unactivated Aryl Chlorides under Mild Conditions by Using Diisopropylaminoborane as a Borylating Reagent

“…Since then, our research has focused on extending the use of such aminoboranes to explore simple syntheses of boron derivatives 7c. d, 11a, c, 12, 13…”

“…Since 2003, aminoboranes have been used as borylation agents in palladium-catalyzed transformations of aryl bro-mides, iodides, and triflates (Scheme 1). [11] We recently extended the use of such aminoboranes for the direct synthesis of biaryl compounds, [12] and also employed aminoboranes in iron-, [7c] zirconium-, [7d] and titanium-catalyzed [7d] borylation of arenediazonium salts. In these reactions, BH 2 NiPr 2 1, which is readily prepared by the thermally-induced dehydrogenation of a diisopropylamine-borane complex, was used.…”

“…, entries[10][11][12][13]. Additionally, sterically hindered aryl chlorides bearing multiple substituents (2 o, 2 p, 2 t, and 2 u) afforded the desired ester compounds 4 o, 4 p, 4 t, and 4 u in 76 to 97 % yield…”

Aminoborylation/Suzuki–Miyaura tandem cross coupling of aryl iodides as efficient and selective synthesis of unsymmetrical biaryls

“…In our program focused on boron chemistry, [23][24][25][26][27][28] we thought about using aminoarylboranes 3 as a reagent for Suzuki Miyaura cross coupling. These compounds are simply prepared through palladium catalysed borylation of aryl halides and triflates with diisopropylaminoborane 1.…”