7163-95-3Relevant academic research and scientific papers
Selective Coupling of 1,2-Bis-Boronic Esters at the more Substituted Site through Visible-Light Activation of Electron Donor–Acceptor Complexes
Aggarwal, Varinder K.,Noble, Adam,Wang, Hui,Wu, Jingjing
, (2022/03/14)
1,2-Bis-boronic esters are useful synthetic intermediates particularly as the two boronic esters can be selectively functionalized. Usually, the less hindered primary boronic ester reacts, but herein, we report a coupling reaction that enables the reversal of this selectivity. This is achieved through the formation of a boronate complex with an electron-rich aryllithium which, in the presence of an electron-deficient aryl nitrile, leads to the formation of an electron donor–acceptor complex. Following visible-light photoinduced electron transfer, a primary radical is generated which isomerizes to the more stable secondary radical before radical-radical coupling with the arene radical-anion, giving β-aryl primary boronic ester products. The reactions proceed under catalyst-free conditions. This method also allows stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to provide trans-substituted products, complementing the selectivity observed in the Suzuki–Miyaura reaction.
Enabling the Cross-Coupling of Tertiary Organoboron Nucleophiles through Radical-Mediated Alkyl Transfer
Primer, David N.,Molander, Gary A.
supporting information, p. 9847 - 9850 (2017/08/02)
The construction of quaternary centers is a common challenge in the synthesis of complex materials and natural products. Current cross-coupling strategies that can be generalized for setting these centers are sparse and, when known, are typically predicated on the use of reactive organometallic reagents. To address this shortcoming a new, photoredox-Ni dual catalytic strategy for the cross-coupling of tertiary organoboron reagents with aryl halides is reported. In addition to details on the cross-coupling scope and limitations, full screening efforts and mechanistic experiments are communicated.
Synthesis of substituted adamantylzinc reagents using a Mg-insertion in the presence of ZnCl2 and further functionalizations
Saemann, Christoph,Dhayalan, Vasudevan,Schreiner, Peter R.,Knochel, Paul
supporting information, p. 2418 - 2421 (2014/05/20)
The LiCl-mediated Mg-insertion in the presence of ZnCl2 allows an efficient synthesis of adamantylzinc reagents starting from the corresponding functionalized tertiary bromides. The highly reactive adamantylzinc species readily undergo a broad
