29689-80-3Relevant articles and documents
Photosensitizer-Free Visible-Light-Mediated Gold-Catalyzed 1,2-Difunctionalization of Alkynes
Huang, Long,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 4808 - 4813 (2016/04/19)
Under visible-light irradiation, the gold-catalyzed intermolecular difunctionalization of alkynes with aryl diazonium salts in methanol affords a variety of α-aryl ketones in moderate to good yields. In contrast to previous reports on gold-catalyzed reactions that involve redox cycles, no external oxidants or photosensitizers are required. The reaction proceeds smoothly under mild reaction conditions and shows broad functional-group tolerance. Further applications of this method demonstrate the general applicability of the arylation of a vinyl gold intermediate instead of the commonly used protodemetalation step. This step provides facile access to functionalized products in one-pot processes. With a P,N-bidentate ligand, a stable aryl gold(III) species was obtained, which constitutes the first direct experimental evidence for the commonly postulated direct oxidative addition of an aryl diazonium salt to a pyridine phosphine gold(I) complex.
AN INTERPRETATION OF THE SUBSTITUENT EFFECT IN THE BLAISE REARRANGEMENT IN TERMS OF PI-ORBITALS
Abe, Yukio,Suehiro, Tadashi
, p. 389 - 392 (2007/10/02)
The migratory aptitude of the substituent groups in the Blaise rearrangement can be explained in terms of the pi-electronic properties of the groups in the highest occupied molecular orbitals.The rates of the rearrangement reaction with relation to the substituent groups were also rationally understood based on the energy levels of the molecular orbitals.
