70557-99-2Relevant articles and documents
PREPARATION OF HALOMETHANEBORONATES
Wuts, Peter G. M.,Thompson, Paul A.
, p. 137 - 142 (1982)
A facile preparation of iodomethaneboronic esters is described.The key step utilizes a tin hydride reduction of dichloromethaneboronic esters.
Methyl Radical Initiated Kharasch and Related Reactions
Tappin, Nicholas D. C.,Renaud, Philippe
supporting information, p. 275 - 282 (2020/12/07)
An improved procedure to run halogen atom and related chalcogen group transfer radical additions is reported. The procedure relies on the thermal decomposition of di-tert-butylhyponitrite (DTBHN), a safer alternative to the explosive diacetyl peroxide, to produce highly reactive methyl radicals that can initiate the chain process. This mode of initiation generates byproducts that are either gaseous (N2) or volatile (acetone and methyl halide) thereby facilitating greatly product purification by either flash column chromatography or distillation. In addition, remarkably simple and mild reaction conditions (refluxing EtOAc during 30 minutes under normal atmosphere) and a low excess of the radical precursor reagent (2 equivalents) make this protocol particularly attractive for preparative synthetic applications. This initiation procedure has been demonstrated with a broad scope since it works efficiently to add a range of electrophilic radicals generated from iodides, bromides, selenides and xanthates over a range of unactivated terminal alkenes. A diverse set of radical trap substrates exemplifies a broad functional group tolerance. Finally, di-tert-butyl peroxyoxalate (DTBPO) is also demonstrated as alternative source of tert-butoxyl radicals to initiate these reactions under identical conditions which gives gaseous by-products (CO2). (Figure presented.).
Total synthesis of virgatolide B
Hume, Paul A.,Furkert, Daniel P.,Brimble, Margaret A.
supporting information, p. 4588 - 4591 (2013/09/24)
The first total synthesis of the benzannulated spiroketal virgatolide A is presented. Key features include sp3-sp2 Suzuki coupling of an enantiomerically enriched β-trifluoroboratoamide and an aryl bromide, regioselective intramolecular carboalkoxylation, and a 1,3-anti-selective Mukaiyama aldol reaction followed by global deprotection/cyclization with regioselectivity governed by internal hydrogen bonding.
