28467-40-5Relevant academic research and scientific papers
Kinetic resolution of chiral cyclohex-2-enones by rhodium(I)/binap- catalyzed 1,2- and 1,4-additions
Kolb, Andreas,Hirner, Sebastian,Harms, Klaus,Zezschwitz, Paultheo Von
supporting information; experimental part, p. 1978 - 1981 (2012/06/18)
The feasibility of kinetic resolutions of racemic monosubstituted cyclohex-2-enones by Rh/binap-catalyzed reactions was investigated. 1,2-Addition of AlMe3 to the 5-substituted derivatives furnished allylic alcohols in the matched case, while t
Annulation Based on 6-Endo-Trig Radical Cyclization: Regioselectivity and Diastereoselectivity
Ward, Dale E.,Gai, Yuanzhu,Kaller, Brian F.
, p. 7830 - 7836 (2007/10/03)
The development of a annulation strategy based on sequential "two-electron" and "one-electron" allylation of β-substituted aldehydes and derivatives with the bifunctional isobutene conjunctive reagent 1 is described.The key step involves an unusual 6-endo-trig radical cyclization.Yields of 6-endo products are improved if the PhS group is oxidized to a PhSO2 group prior to cyclization.The structural factors affecting the regioselectivity and stereoselectivity of the cyclization are examined.In general, the stereoselectivity of 6-endo-trig cyclization of 5-hexenyl radicals can be rationalized by conformational analysis of chairlike transition states and can be calculated effectively with an MM2 force field model.High 6-endo regioselectivity requires a strong driving force.Fragmentable allylic groups (R3Sn, PhSO2, and to a lesser extent PhS) are shown to be sufficiently activating to achieve 6-endo regioselectivity.
Chemistry of Higher Order, Mixed Organocuprates. 5. On the Choice of the Copper(I) Salt for the Formation of R2CuLi
Lipshutz, Bruce H.,Kozlowski, Joseph A.,Wilhelm, Robert S.
, p. 546 - 550 (2007/10/02)
Chemical and spectroscopic studies are presented that have been designed to manifest differences in reagent composition and reactivity between mixtures of CuI/2RLi and CuSCN/2RLi.The results indicate that while both Cu(I) salts are reported to serve as precursors to lower order cuprates R2CuLi, CuSCN may actually be forming a higher order, mixed species R2Cu(SCN)Li2.This would explain the discrepancy in coupling reactions of each solution with similar organic substrates under otherwise identical conditions.The presence of added lithium salts demonstrates that while Li I added to CuSCN/2RLi has essentially no effect, introduction of an equivalent of LiSCN to CuI/2RLi dramatically alters the efficiency of ligand transfer.
