1374563-43-5Relevant academic research and scientific papers
Rhodium dinaphthocyclooctatetraene complexes: Synthesis, characterization and catalytic activity in [5+2] cycloadditions
Wender, Paul A.,Lesser, Adam B.,Sirois, Lauren E.
supporting information; experimental part, p. 2736 - 2740 (2012/04/23)
Rh COT in the act: A Ni0-catalyzed [2+2+2+2] cycloaddition provides a high-yielding, scalable synthesis of the ligand dinaphtho[a,e] cyclooctatetraene (dnCOT). dnCOT complexation with RhI gives [Rh(dnCOT)(MeCN)2]SbF6
Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory
Liu, Peng,Sirois, Lauren E.,Cheong, Paul Ha-Yeon,Yu, Zhi-Xiang,Hartung, Ingo V.,Rieck, Heiko,Wender, Paul A.,Houk
supporting information; experimental part, p. 10127 - 10135 (2010/10/04)
The first studies on the regioselectivity of Rh(I)-catalyzed (5 + 2) cycloadditions between vinylcyclopropanes (VCPs) and alkynes have been conducted experimentally and analyzed using density functional theory (DFT). The previously unexplored regiochemical consequences for this catalytic, intermolecular cycloaddition were determined by studying the reactions of several substituted VCPs with a range of unsymmetrical alkynes. Experimental trends were identified, and a predictive model was established. VCPs with terminal substitution on the alkene reacted with high regioselectivity (>20:1), as predicted by a theoretical model in which bulkier alkyne substituents prefer to be distal to the forming C-C bond to avoid steric repulsions. VCPs with substitution at the internal position of the alkene reacted with variable regioselectivity (ranging from >20:1 to a reversed 1:2.3), suggesting a refined model in which electron-withdrawing substituents on the alkyne decrease or reverse sterically controlled selectivity by stabilizing the transition state in which the substituent is proximal to the forming C-C bond.
