104367-27-3Relevant articles and documents
Mechanistic study of gold(l)-catalyzed lntermolecular hydroamination of alienes
Jane Wang,Benltez, Diego,Tkatchouk, Ekaterina,Goddard III, William A.,Dean Toste
, p. 13064 - 13071 (2010)
The intermolecular hydroamination of alienes occurs readily with hydrazlde nucleophlles, In the presence of 3-12% Ph3PAuNTf2. Mechanistic studies have been conducted to establish the resting state of the gold catalyst, the kinetic order of the reaction, the effect of ligand electronics on the overall rate, and the reversibility of the last steps in the catalytic cycle. We have found the overall reaction to be first order In gold and aliene and zero order in nucleophile. Our studies suggest that the rate-limiting transition state for the reaction does not involve the nucleophile and that the active catalyst Is monomeric in gold(l). Computational studies support an outersphere mechanism and predict that a two-step, no intermediate mechanism may be operative. In accord with this mechanistic proposal, the reaction can be accelerated with the use of more electron-deficient phosphine ligands on the gold(l) catalyst.
Rhodium-Catalyzed Parallel Kinetic Resolution of Racemic Internal Allenes Towards Enantiopure Allylic 1,3-Diketones
Hilpert, Lukas J.,Breit, Bernhard
supporting information, p. 9939 - 9943 (2019/06/24)
A rare case of a parallel kinetic resolution of racemic 1,3-disubstituted allenes by means of a rhodium-catalyzed addition to 1,3-diketones furnishing enantiopure allylic 1,3-diketones is described. Mechanistic experiments demonstrate that the different allene enantiomers react in parallel to either the diastereomeric E- or Z-allylic 1,3-diketones with the same absolute configuration of the newly formed stereogenic center. A broad substrate scope demonstrates the synthetic utility of this new method.
Z-Selective Hydrothiolation of Racemic 1,3-Disubstituted Allenes: An Atom-Economic Rhodium-Catalyzed Dynamic Kinetic Resolution
Pritzius, Adrian B.,Breit, Bernhard
supporting information, p. 15818 - 15822 (2016/01/29)
A Z-selective rhodium-catalyzed hydrothiolation of 1,3-disubstituted allenes and subsequent oxidation towards the corresponding allylic sulfones is described. Using the bidentate 1,4-bis(diphenylphosphino)butane (dppb) ligand, Z/E-selectivities up to >99:1 were obtained. The highly atom-economic desymmetrization reaction tolerates functionalized aromatic and aliphatic thiols. Additionally, a variety of symmetric internal allenes, as well as unsymmetrically disubstituted substrates were well tolerated, thus resulting in high regioselectivities. Starting from chiral but racemic 1,3-disubstituted allenes a dynamic kinetic resolution (DKR) could be achieved by applying (S,S)-Me-DuPhos as the chiral ligand. The desired Z-allylic sulfones were obtained in high yields and enantioselectivities up to 96 % ee.