Chemistry of Group 13 element-transition metal linkage — the platinum- and palladium-catalyzed reactions of (alkoxo)diborons

Abstract

The metal-catalyzed borylation of alkenes, alkynes, and organic electrophiles with B-B compounds was developed for the synthesis of and allyl chlorides or acetates was found to yield aryl-, vinyl-, and allylboronates in high yields in the presence of a base and a palladium catalyst, which provides the first one-step procedure for the synthesis of organoboronic esters from organic electrophiles under mild conditions. The mechanisms and the synthetic applications of these reactions are discussed.2

Synthesis of pinacol arylboronates via cross-coupling reaction of bis(pinacolato)diboron with chloroarenes catalyzed by palladium(0)–tricyclohexylphosphine complexes

“…97, 83.38, 104.50, 113.96, 121.30, 124.58, 127.84, 132.49, 135. Syntheses of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene (entry 1), 1,8 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene (entry 2), -dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (entry 13), 1,8 and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) …”

“…1 The coupling reaction is feasible with various functional groups, e.g., CO 2 Me, COMe, NO 2 , and CN, which need protection-deprotection in the two-step procedure for preparing arylboronic acids or esters from magnesium or lithium reagents. 2 The protocol offers a direct and efficient route to variously functionalized boronic esters, the utility of which has been amply demonstrated in the synthesis of natural products, 3 biologically active compounds, 4 and functional materials.…”

Biaryl Product Formation from Cross-coupling in Palladiumcatalyzed Borylation of a Boc Protected Aminobromoquinoline Compound

“…The first method was used to prepare 8-QBA in 1959 [29], but is not compatible with certain sensitive functional groups such as nitro, amide, amine, and hydroxy. The latter coupling reaction can tolerate various functional groups and has been widely applied to the synthesis of arylboronic esters in one step [30]. Therefore, the palladium-catalyzed cross-coupling reaction was chosen for the preparation of monoboronic acid 2 (Scheme 1).…”

“…The resulting solution was further stirred for 12 h, then the methanol was evaporated and the residue was extracted with EtOAc (3 × 10mL). The combined organic extracts were washed with saturated brine (30 …”

Experimental and DFT studies on poly[octa-μ3-acesulfamato-O,O:N,O′;O′,N:O,O-tetraaquatetrabarium(II)] complex

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The oxidative addition of B-B bonds of diboranes(4) to late transition metal centres affording bis(boryl)complexes [L n M(BR 2 ) 2 ] [1,2] is of great importance because it constitutes the key step in metal-mediated diboration reactions of unsaturated substrates under both homogeneous [3,4] and heterogeneous [5] conditions. Based on facile oxidative addition of B-Br and B-I bonds to Pt(0) centres [6], we became interested in the reactivity of diboranes(4) Br 2 B 2 R 2 (R = NMe 2 , Mes) towards low-valent phosphine platinum complexes.

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