17103-25-2

Upstream product

• 12125-87-0 (methylbenzoate)chromium tricarbonyl 
• 696-62-8 para-iodoanisole 
• 610-94-6 2-bromobenzoic acid methyl ester 
• 201230-82-2 carbon monoxide 
• 79422-15-4 2-(4-methoxyphenyl)-1,3,6,2-dioxazaborocane 
• 5720-07-0 4-methoxyphenylboronic acid 

Downstream Products

• 1286261-77-5 4′-methoxy-N-phenyl-[1,1′-biphenyl]-2-carboxamide 
• 1143-62-0 3-Methoxy-6H-dibenzopyran-6-one 
• 1027504-49-9 5-(4-Methoxy-phenyl)-4H-isoquinoline-3,3-dicarboxylic acid diethyl ester 
• 1026003-67-7 5-(4-Methoxy-phenyl)-1,4-dihydro-2H-isoquinoline-3,3-dicarboxylic acid diethyl ester 
• 170304-68-4 methyl 4'-hydroxy-1,1'-biphenyl-2-carboxylate 
• 157921-29-4 4'-Methoxy-biphenyl-2-carboxylic acid [4-(2,3,4,5-tetrahydro-benzo[b]azepine-1-carbonyl)-phenyl]-amide 
• 18110-71-9 4'-methoxybiphenyl-2-carboxylic acid 
• 67526-82-3 4'-hydroxy-1,1'-biphenyl-2-carboxylic acid 

Relevant academic research and scientific papers

Carbonylative Suzuki-Miyaura couplings of sterically hindered aryl halides: Synthesis of 2-aroylbenzoate derivatives

We have developed a carbonylative approach to the synthesis of diversely substituted 2-aroylbenzoate esters featuring a new protocol for the carbonylative coupling of aryl bromides with boronic acids and a new strategy to favour carbonylative over non-carbonylative reactions. Two different synthetic pathways-(i) the alkoxycarbonylation of 2-bromo benzophenones and (ii) the carbonylative Suzuki-Miyaura coupling of 2-bromobenzoate esters-were evaluated. The latter approach provided a broader substrate tolerance, and thus was the preferred pathway. We observed that 2-substituted aryl bromides were challenging substrates for carbonylative chemistry favouring the non-carbonylative pathway. However, we found that carbonylative Suzuki-Miyaura couplings can be improved by slow addition of the boronic acid, suppressing the unwanted direct Suzuki coupling and, thus increasing the yield of the carbonylative reaction.

Arene-metal π-complexation as a traceless reactivity enhancer for C-H arylation

Current approaches to facilitate C-H arylation of arenes involve the use of either strongly electron-withdrawing substituents or directing groups. Both approaches require structural modification of the arene, limiting their generality. We present a new approach where C-H arylation is made possible without altering the connectivity of the arene via π-complexation of a Cr(CO)3 unit, greatly enhancing the reactivity of the aromatic C-H bonds. We apply this approach to monofluorobenzenes, highly unreactive arenes, which upon complexation become nearly as reactive as pentafluorobenzene itself in their couplings with iodoarenes. DFT calculations indicate that C-H activation via a concerted metalation-deprotonation transition state is facilitated by the predisposition of C-H bonds in (Ar-H)Cr(CO)3 to bend out of the aromatic plane.