74226-59-8Relevant articles and documents
Highly selective one-pot synthesis of spirophosphoranes exhibiting reversed apicophilicity by oxidation of dianions generated from P-H spirophosphorane
Kajiyama, Kazumasa,Yoshimune, Miki,Nakamoto, Masaaki,Matsukawa, Shiro,Kojima, Satoshi,Akiba, Kin-Ya
, p. 1873 - 1875 (2001)
(formula presented) Mild and highly selective one-pot procedures for obtaining phosphoranes that exhibit reversed (O-cis) apicophilicity are described. On the basis of the procedures, O-cis phosphorane bearing an aryl group (R = 2,4,6-tri-i-propylphenyl)
1,2-Boron Shifts of β-Boryl Radicals Generated from Bis-boronic Esters Using Photoredox Catalysis
Kaiser, Daniel,Noble, Adam,Fasano, Valerio,Aggarwal, Varinder K.
supporting information, p. 14104 - 14109 (2019/10/11)
1,2-Bis-boronic esters are versatile intermediates that enable the rapid elaboration of simple alkene precursors. Previous reports on their selective mono-functionalization have targeted the most accessible position, retaining the more hindered secondary boronic ester. In contrast, we have found that photoredox-catalyzed mono-deboronation generates primary β-boryl radicals that undergo rapid 1,2-boron shift to form thermodynamically favored secondary radicals, allowing for selective transformation of the more hindered boronic ester. The pivotal 1,2-boron shift, which has been demonstrated to be stereoretentive, enables access to a wide range of functionalized boronic esters and has been applied to highly diastereoselective fragmentation and transannular cyclization reactions. Furthermore, its generality has been shown in a radical cascade reaction with an allylboronic ester.
