51575-80-5Relevant articles and documents
Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
supporting information, p. 3466 - 3471 (2021/05/31)
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
HIGH-PRESSURE INITIATED SYNTHESIS OF DOMINICALURES 1 AND 2 BY THE BAYLIS-HILLMAN METHOD
Moiseenkov, A. M.,Cheskis, B. A.,Shpiro, N. A.,Stashina, G. A.,Zhulin, V. M.
, p. 517 - 521 (2007/10/02)
The dimerization of methyl acrylate to dimethyl α-methyleneglutarate by the action of tributylphosphine in the absence of a solvent was investigated.Methyl α-methylene-β-hydroxypentanoate was obtained with a moderate yield by the condensation of propionaldehyde with methyl acrylate catalyzed by triphenylphosphine or 1,4-diazabicyclooctane and initiated by high pressure.In the last of these data a three-stage stereospecific synthesis of dominicalures 1 and 2 (components of the aggregation pheromone of the grain beetle) was realized from sec-amyl acrylate and propionaldehyde or isobutyraldehyde.
