65322-32-9Relevant academic research and scientific papers
Silylium-Ion-Promoted (5+1) Cycloaddition of Aryl-Substituted Vinylcyclopropanes and Hydrosilanes Involving Aryl Migration
Bonetti, Vittorio,He, Tao,Klare, Hendrik F. T.,Oestreich, Martin,Wang, Guoqiang
supporting information, p. 12186 - 12191 (2020/05/22)
A transition-metal-free (5+1) cycloaddition of aryl-substituted vinylcyclopropanes (VCPs) and hydrosilanes to afford silacyclohexanes is reported. Catalytic amounts of the trityl cation initiate the reaction by hydride abstraction from the hydrosilane, and further progress of the reaction is maintained by self-regeneration of the silylium ions. The new reaction involves a [1,2] migration of an aryl group, eventually furnishing 4- rather than 3-aryl-substituted silacyclohexane derivatives as major products. Various control experiments and quantum-chemical calculations support a mechanistic picture where a silylium ion intramolecularly stabilized by a cyclopropane ring can either undergo a kinetically favored concerted [1,2] aryl migration/ring expansion or engage in a cyclopropane-to-cyclopropane rearrangement.
B(C6F5)3-Catalyzed Hydrosilylation of Vinylcyclopropanes
He, Tao,Long, Peng-Wei,Oestreich, Martin
supporting information, p. 7383 - 7386 (2020/10/12)
A hydrosilylation of vinylcyclopropanes (VCPs) catalyzed by the strong boron Lewis acid B(C6F5)3 is reported. For the majority of VCPs, little or no ring opening of the cyclopropyl unit is observed. Conversely, for VCPs with bulky R groups, such as ortho-substituted aryl rings or branched alkyl residues, ring opening is the exclusive reaction pathway. This finding is explained by the thwarted hydride delivery to a sterically shielded, β-silicon-stabilized cyclopropylcarbinyl cation intermediate.
A Stereoconvergent Cyclopropanation Reaction of Styrenes
del Hoyo, Ana M.,Herraiz, Ana G.,Suero, Marcos G.
supporting information, p. 1610 - 1613 (2017/02/05)
The first stereoconvergent cyclopropanation reaction by means of photoredox catalysis using diiodomethane as the methylene source is described. This transformation exhibits broad functional group tolerance and it is characterized by an excellent stereocontrol en route to trans-cyclopropanes regardless of whether E- or Z-styrene substrates were utilized.
Difluoroalkylation/C-H Annulation Cascade Reaction Induced by Visible-Light Photoredox Catalysis
Li, Jin,Chen, Jingzhi,Jiao, Wei,Wang, Guoqiang,Li, Ying,Cheng, Xu,Li, Guigen
, p. 9992 - 10001 (2016/10/31)
We report the first example of difluoroalkylation/C-H annulation cascade reactions of cyclopropyl olefins induced by visible-light photoredox catalysis regioselectively affording partially hydrogenated naphthalenes and quinolines with a variety of difluorinated side chains. The alkylation reagent could be extended to monofluoro and trifluoro reagents, nitrile and malonate. The regioselectivity was investigated by means of density functional theory calculations.
