＜正＞The transition metal catalyzed reactions of diazo compounds have been well-established as powerful approach...
Lei Zhou,Fei Ye,Yan Zhang and Jianbo Wang~* Beijing National Laboratory for Molecular Sciences(BNLMS),Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry,Peking University,Beijing 100871,China
A Pd（II） catalyzed tandem reaction of o-alkynylbenzaldehydes or o-alkynylbenzaldimines with substituted indoles initiated by the intermolecular addition of indoles to the carbonyl or imine group followed by the nucleopalladation of an intramolecular alkyne and quenching the carbon-palladium bond by protonolysis to regenerate the Pd（II） species was developed. The reaction can be carried out under mild conditions without the necessity of a redox system.
In the past decade, the asymmetric Morita-Baylis-Hillman (MBH)/aza-Morita-Baylis-Hillman (aza-MBH) reaction has attracted great attention because it leads to the formation of densely functionalized products in a catalytic and atom-economic way. The MBH/aza-MBH adducts can be further applied in a wide variety of organic synthesis, such as peptide synthesis and heterocyclic compounds synthesis. After a lot of attempts to improve the enantioselectivity, many types of chiral organocatalysts have been identified as highly enantioselective organocatalysts in MBH/aza-MBH reaction. Especially, certain "privileged chiral catalysts" are highly enantioselective in MBH/aza-MBH reaction, which are designed and developed through introducing bi-/multi-functional groups on the so-called "privileged structures" such as cinchona alkaloids, BINAP/BINOL. This review summarizes the exciting advances about the design and development of chiral catalysts derived from "privileged structures" and their applications in asymmetric MBH/aza-MBH reaction.
＜正＞Epoxides are highly versatile intermediates in organic synthesis due to their easy access and their suscept...
Tao Wang and Junliang Zhang~* Shanghai Key Laboratory of Green Chemistry and Chemical Processes,Department of Chemistry, East China Normal University,200062
A unique transformation to realize the allylic amination from vinylic bromides was described and an unexpected C-Pd migration was observed from sp2 carbon to adjacent allylic sp3 carbon initiated from vinyl bromide. Various 3-aryl-2-bromopropenes and secondary amines were surveyed and the allyl amination products were obtained in moderate isolated yields. The primary amine was not fit for this transformation. Mechanistic studies indicate that this migration went through β-hydride elimination and reverse C=C bond insertion.
