150033-80-0

Usage

Uses

Used in Organic Synthesis:
4-(Methoxycarbonyl)benzylboronic Acid Pinacol Ester is used as a versatile building block for the preparation of various pharmaceuticals, agrochemicals, and materials. Its reactivity with different electrophiles and nucleophiles makes it a valuable component in the synthesis of complex organic molecules.
Used in Palladium-Catalyzed Cross-Coupling Reactions:
4-(Methoxycarbonyl)benzylboronic Acid Pinacol Ester has been studied for its potential use in palladium-catalyzed cross-coupling reactions. It has shown promising results as a reagent in such processes, contributing to the formation of new carbon-carbon bonds and the synthesis of advanced organic compounds.

Upstream product

• 34040-64-7 p-methyloxycarbonylbenzyl chloride 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 2417-72-3 Methyl 4-(bromomethyl)benzoate 
• 73183-34-3 bis(pinacol)diborane 
• 619-42-1 4-methoxycarbonylphenyl bromide 
• 129422-12-4 ((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)zinc(II) iodide 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 745783-97-5 triethyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 
• 166330-03-6 pinacol (bromomethyl)boronate 
• 619-44-3 methyl 4-iodobenzoate 

Relevant academic research and scientific papers

Nucleophilic borylation of benzyl halides with bis(pinacolato)diboron catalyzed by palladium(0) complexes

Nucleophilic borylation of benzyl halides with bis(pinacolato)diboron in the presence of KOAc in toluene was effectively catalyzed by a palladium complex generated in situ from Pd(dba)2 and (4-MeOC6H4)3P, giving the corresponding pinacol benzylboronates in high yields.

Photochemical Radical C–H Halogenation of Benzyl N-Methyliminodiacetyl (MIDA) Boronates: Synthesis of α-Functionalized Alkyl Boronates

α-Haloboronates are useful organic synthons that can be converted to a diverse array of α-substituted alkyl borons. Methods to α-haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C-H halogenation of benzyl N-methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C?Br bond in the brominated product could be readily transformed to a series of C?C, C?O, C?N, C?S, C?P, and C?I bonds, some of which are difficult to forge with α-halo sp2-B boronate esters. An activation effect of B(MIDA) moiety was found.

Regioselective α-benzylation of 3-iodoazetidine via Suzuki cross-coupling

An efficient protocol for the synthesis of α-benzyl azetidines starting from benzylboronic acid pinacol ester derivatives and 3-iodoazetidine was developed. A wide range of α-benzyl azetidine derivatives were obtained in moderate to good yields with high regioselectivity (>99%).

Nickel-Catalyzed Umpolung Arylation of Ambiphilic α-Bromoalkyl Boronic Esters

A nickel-catalyzed reductive arylation of ambiphilic α-bromoalkyl boronic esters with aryl halides is described. This platform provides an unrecognized opportunity to promote the catalytic umpolung reactivity of ambiphilic reagents with aryl halides, thus unlocking a new cross-coupling strategy that complements existing methods for the preparation of densely functionalized alkyl-substituted organometallic reagents from simple and readily accessible precursors.

Iridium-Catalyzed Borylation of Primary Benzylic C-H Bonds without a Directing Group: Scope, Mechanism, and Origins of Selectivity

Primary benzylic boronate esters are useful intermediates in organic synthesis, but these reagents cannot be prepared by hydroboration. The benzylic C-H borylation of methylarenes would be a method to form these products, but such reactions without neat methylarene or a directing group are unknown. We report an approach to divert the borylation of methylarenes from aromatic positions to benzylic positions with a silylborane as reagent and a new iridium catalyst containing an electron-deficient phenanthroline as ligand. This system forms benzylic boronate esters selectively over the corresponding aryl boronate esters. An Ir diboryl monosilyl complex ligated by the phenanthroline was isolated and determined to be the resting state of the catalyst. Mechanistic studies show that this complex is kinetically competent to be an intermediate in the catalytic process. Kinetic studies of benzylic and aryl C-H borylation catalyzed by various Ir complexes show that the rate of aryl C-H borylation decreases with decreasing electron density at the metal center of the Ir catalyst, but that the rate of benzylic C-H borylation is less sensitive to the degree of electron density at the metal center of the Ir catalyst. Kinetic and computational studies suggest that the two borylation reactions respond differently to the degree of electron density at the metal center because they occur with different turnover-limiting steps. The turnover-limiting step in the borylation of aryl C-H bonds is known to be C-H oxidative addition, but the turnover-limiting step of the borylation of benzylic C-H bonds appears to be an isomerization prior to C-B reductive elimination.

Synthesis of benzylboronates via palladium-catalyzed borylation of benzyl halides with pinacolborane

Various benzyl halides were borylated with pinacolborane in the presence of iPr2NEt and a catalytic amount of PdCl2(PPh3)2 to afford the corresponding benzylboronates in good yields.

Synthesis of ortho-Acylbenzylboronates via Cross-Coupling Reaction of (Dialkoxyboryl)methylzinc Reagents with Haloarenes. A Stable ortho-Quinodimethane Precursor

The cross-coupling reaction of IZnCH2B(OCMe2)2 with iodoarenes in the presence of PdCl2(PPh3)2 produces the corresponding benzylic boronates in high yields.Among them, the benzylic boronates having an acyl group at the ortho position readily undergo the 1,5-rearrangement to the carbonyl oxygen producing the o-quinodimethane derivatives under thermal or photochemical conditions.The reaction provides benzo-fused cycloalkanes by trapping with dienophiles.cross