Wen-Jun Zhou

Limited research has been conducted on the exploration of chemical reactions in deep eutectic solvents (DES) using density functional theory (DFT). In this study, a comprehensive analysis of the mechanism of a cross-aldol reaction in DES through DFT calculations at the M06-2X/6-311+G(d,p)//M06-2X/6-31G(d,p) level was carried out for the first time. The aldol reaction mechanism comprised two primary stages, namely, enolization and addition, with the former identified as the rate-determining step. In this paper, an explicit explanation of the functions of catalysts, solvents and water, with results that aligned well with experimental findings, has been provided. The theoretical analysis indicated that the –COOH group of the catalyst could enhance the stability of transition states by forming a polygonal reaction center, compared to the –OH group or water, thus favoring the reaction process. The increased susceptibility of the catalyst was attributed to the enhanced ionization of the proton in the –COOH group. Findings from the IGM analysis indicated that the stability of the system was enhanced through the formation of hydrogen bonds (HBs), resulting from the interaction between DES and the substrates. It was also noted that the number of HBs did not directly correlate with the system's stability. Notably, the most stable configuration involved the disruption of the solvent structure when DES interacted with the reactants. The introduction of water compensated for the solvent's deficiency by forming new O–H⋯Cl bonds, leading to the formation of additional hydrogen bonds and thereby enhancing the system's stability. Furthermore, the impact of substituent groups was evident through the formation of an O–H⋯O_NO bond, which was generated by the interaction between ethylene glycol and the –NO₂ group. The substituent effect played a crucial role in the reaction and elucidated the necessity of solvent disruption. The computational analysis revealed an increase in the energy barrier when the –NO₂ group was substituted with –H, –Cl and –Br. In addition, the study offered a comprehensive understanding of the influence of DES and the role of the additional third component in the reaction.

A chiral phosphoric acid (CPA)-catalyzed asymmetric [3 + 3] cycloaddition of cinnamaldehyde-derived nitrones with 2-indolylmethanols was developed to prepare various indole-fused 1,2-oxazines in high yields with excellent enantioselectivity.

Catalytic reductive coupling of two electrophiles and one unsaturated bond represents an economic and efficient way to construct complex skeletons, which is dominated by transition-metal catalysis via two electron transfer. Herein, we report a strategy of visible-light photoredox-catalyzed successive single electron transfer, realizing dearomative arylcarboxylation of indoles with CO₂. This strategy avoids common side reactions in transition-metal catalysis, including ipso-carboxylation of aryl halides and β-hydride elimination. This visible-light photoredox catalysis shows high chemoselectivity, low loading of photocatalyst, mild reaction conditions (room temperature, 1 atm) and good functional group tolerance, providing great potential for the synthesis of valuable but difficultly accessible indoline-3-carboxylic acids. Mechanistic studies indicate that the benzylic radicals and anions might be generated as the key intermediates, thus providing a direction for reductive couplings with other electrophiles, including D₂O and aldehyde.

Palladium-catalyzed carbon-carbon and carbon-heteroatom bond construction are among the most significant and powerful methods in organic synthesis. Numerous works are focusing on the application and development of the ground-state reactivity of palladium catalyst. Recently, visible light-induced palladium catalysis has been reported to enable some unprecedented transformations via the photoexcited-state of the palladium complex, which could not be achieved under traditional thermal conditions. This highlight review discusses the recent progress in this sort of novel synthetic methods.

Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C–C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C–N bonds, undergo selective couplings with aldehydes/ketone and CO₂. Notably, the in situ generated byproduct, trimethylamine, is efficiently utilized as the electron donor. Moreover, this protocol exhibits mild reaction conditions, low catalyst loading, broad substrate scope, good functional group tolerance, and facile scalability. Mechanistic studies indicate that benzyl radicals and anions might be generated as the key intermediates via photocatalysis, providing a new direction for cross-electrophile couplings.

The following mistakes have been corrected for the final online and print version:In Scheme 2 and 8, 'Nickle' was replaced by 'Nickel'.In Scheme 3, was replaced by and '77%' was replaced by '73%'. In Scheme 4, '84%' was replaced by '69%' and '28%' was replaced by '26%'.In Scheme 7, was replaced by and 'Boc' was replaced by 'Bac'. In Scheme 7, '68%' was replaced by '66%'. Scheme 8 was replaced by In Scheme 9, 'R1O' was replaced by 'R1', 'R1 = Ts, Tf, P(O)Ph2' was replaced by 'R1 = OTs, OTf, OP(O)Ph2' and 'R1 = P(O)Ph2, 61% yield' was replaced by 'R1 = OP(O)Ph2, 61% yield'.In Scheme 10, was replaced by In Scheme 11, '82%' was replaced by '74%'.In Scheme 14, '54%' was replaced by '40%'.In Scheme 20, the 't-Bu' group was replaced by a 'n-Bu' group. In Scheme 25, was replaced by In Scheme 35, one 'Me' group was replaced by a 't-Bu' group.In Scheme 36, '79%' was replaced by '89%'.In Scheme 41, '64%' was replaced by '90%'.In Scheme 42, '13%' was replaced by '17%'.In Scheme 45, '61%' was replaced by '71%'. In Scheme 46, was replaced by On page 3376, the following text was added: 'Recently, during the investigation on photoinduced copper-catalyzed C–H functionalization,55 Ackermann and coworkers55a disclosed an elegant example of visible-light-induced direct C–H arylation by merging of iridium photoredox catalysis with copper catalysis (Scheme 43).'Scheme 43 was added.The following reference was added: '(55) (a) Yang, F.; Koeller, J.; Ackermann, L. Angew. Chem. Int. Ed. 2016, 55, 4759. (b) Gandeepan, P.; Mo, J.; Ackermann, L. Chem. Commun. 2017, 53, 5906.' Synthesis, 2018, 50, 3359