Metal-Catalyzed Reactions of Organoboronic Acids and Esters

Abstract

Metal-catalyzed B-C and C-C bond-forming reactions of organoboronic acids that have been pursued in the past three decades by our group are summarized in this article. B-C bond-forming reactions for the synthesis of organoboronic acid derivatives include metal-catalyzed addition reactions of pinacolborane or catecholborane (hydroboration), bis(pinacolato)diboron (diboration), and alkylthioboranes (thioboration) to alkenes, alkynes, 1,3-alkadienes, or 1,2-alkadienes (allenes). Other B-C bond-forming reactions include coupling reactions of pinacolborane or bis(pinacolato)diboron for borylation of C-halogen bonds with palladium catalysts and C-H bonds of arenes and alkenes with iridium catalysts. These reactions have provided a convenient new access to aryl-, 1-alkenyl-, allyl-, or benzylboronates. Metal-catalyzed C-C and C-N bond-forming reactions using boronic acid derivatives include synthesis of novel cyclic triolborate salts for palladium-or copper-catalyzed cross-coupling reactions with organic halides or amines, rhodium-or palladiumcatalyzed 1,4-addition reactions of arylboronic acids to ,-unsaturated carbonyl compounds and rhodium-catalyzed addition of aryl-and 1-alkenylboronic acids to aldehydes and imines.

Molecular‐Architecture‐Based Administration of Catalysis in Water: Self‐Assembly of an Amphiphilic Palladium Pincer Complex

“…[15] Thus, the vesicle 1 vscl (2 mol % Pd) catalyzed the Miyaura-Michael reaction of cyclohexenone (6) with sodium tetraphenylborate (8 a, 1.5 equiv) in water to give the desired arylated product 9 a in 83 % yield with 98 % reaction selectivity after 12 hours (entry 1), whereas the amorphous 1 amps afforded only a 7 % yield of 9 a with much lower selectivity (entry 2). The reaction of cyclohexenone (6) with sodium tetrakis(4-fluorophenyl)borate (8 b) also proceeded to afford 9 b in 63 % yield and 95 % selectivity, whereas 1 amps did not promote the reaction (entries 3 and 4).…”

Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

“…Our next concern was to apply the C(sp 2 )-F bond activation methodology to a Suzuki-Miyaura type C-C bond formation reaction that generally offers the advantages of tolerance across a broad range of functional groups [70][71][72][73][74]. Most of the reported Suzuki-Miyaura type cross-coupling reactions via C-F bond cleavage, employing either highly electron-deficient organofluorine compounds or those bearing a directing group, have traditionally been conducted in the presence of a base [59,[75][76][77][78][79][80][81][82][83][84][85], whereas fluoride anion itself is regarded as a good activator for neutral organoboron reagents.…”

“Greening Up” Cross-Coupling Chemistry

“…The palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl halides and boronic acids has emerged as the method of choice for the synthesis of biaryls [33]. The ubiquity of biaryl targets, both in nature and of unnatural origin [34], has led to dramatic increases in commercial availability of aryl boronic acids and their derivatives.…”