37442-45-8Relevant articles and documents
Reevaluation of the mechanism of the Baylis-Hillman reaction: Implications for asymmetric catalysis
Aggarwal, Varinder K.,Fulford, Sarah Y.,Lloyd-Jones, Guy C.
, p. 1706 - 1708 (2005)
(Chemical Equation Presented) One step beyond: Proton transfer (step 3, see scheme), not C-C bond formation (step 2) as previously thought, is the rate-limiting step (RLS) in the initial stage of the Baylis-Hillman reaction, which involves the amine-catal
Silver/palladium relay catalyzed 1,3-dipole annulation/allylation reactions to access fully substituted allyl imidazolidines
Han, Ruiping,Ding, Yue,Jin, Xueke,Li, Er-Qing
supporting information, p. 646 - 649 (2020/02/11)
A silver/palladium relay catalyzed 1,3-dipole annulation/allylation reaction of iminoesters and Baylis-Hillman acetates for the construction of fully substituted allyl imidazolidines is reported. The reaction of both iminoesters and Baylis-Hillman acetate
On the development of a nucleophilic methylthiolation methodology
Carvalho, Bernardo Basbaum Portinho De Puga,Amaral, Adriane Antonia Pereira,De Castro, Pedro P?ssa,Ferreira, Fernanda Cerqueira Moreira,Horta, Bruno Araújo Cautiero,Amarante, Giovanni Wilson
, p. 5420 - 5426 (2020/08/03)
Methylthiolation reactions are usually explored to access organosulfur compounds using methanethiol, an extremely flammable and toxic compound. Herein, methylthiomethyl esters were successfully applied as novel methylthiolation reagents in a low cost, transition-metal-free methodology. These reagents allowed the methylthiolation of a wide scope of chalcones, acyl ester derivatives and Morita-Baylis-Hillman acetates with good group tolerance, affording the methylthiolated products in moderate to excellent yields. The reaction mechanism was investigated through several control experiments, as well as by theoretical calculations employing Density Functional Theory. The results strongly support that a sulfurane and a sulfonium ylide appear as key intermediates and that a Pummerer type rearrangement is also crucial for the formation of this novel reagent. Furthermore, the methylthiolation mechanism is likely to proceed through the nucleophilic attack of the reagent, followed by an entropically favoured step involving the acetate attack to the positively charged species, then releasing the product. This journal is
Can Heteroarenes/Arenes Be Hydrogenated Over Catalytic Pd/C Under Ambient Conditions?
Tanaka, Nao,Usuki, Toyonobu
supporting information, p. 5514 - 5522 (2020/07/24)
Hydrogenation of over a dozen aromatic compounds, including both heteroarenes and arenes, over palladium on carbon (Pd/C, 1–100 molpercent) with H2-balloon pressure at room temperature is reported. Analyses using pyridine as a model substrate revealed that acetic acid was the best solvent, as using only 1 molpercent Pd/C provided piperidine quantitatively. Substrate scope analysis and density functional theory calculations indicated that reaction rates are highly dependent on frontier molecular orbital characteristics and the steric bulkiness of substituents. Moreover, the established method was used for the concise synthesis of the anti-Alzheimer drug donepezil (Aricept?).
