镍催化支链1,3-二烯的氢烷基化反应机理探究

随着算法和理论化学的发展,量子化学计算已被用于解释和预测各种化学实验。镍催化共轭烯烃的氢烷基化反应是一类重要的有机化学反应,其机理一直是有机化学家关注的焦点。本文利用密度泛函理论(DFT)对Mazet课题组开发的一个氢烷基化反应进行了详细的研究,得到了该反应可能的机理模型。在此背景下,对反应的极具吸引力的区域选择性进行了探讨和合理解释。

Carbon isotopic compositions of individual terpenoids in heavy oils from Karamay oilfield

The carbon isotopic compositions of individual terpenoids in the heavy oils from the Karamay oilfield were determined by using the method of enrichment of terpanes with molecular sieve 13X and GC-IRMS technique. The terpanes, selectively enriched from the biodegraded oils with molecular sieve 13X, can meet the demand of GO-IRMS analysis. The carbon isotopic compositions of the hopanoids (δ13C-31.7‰—-37.8‰) infer that their main source is probably non-methanotrophic bacteria,and that the depositional environment of source rocks is a strongly reductive, rapidly depositional, and closed-semi-closed saline lagoon.

Mechanistic insights into the rhodium-catalyzed aryl C-H carboxylation

The recently reported Rh(Ⅱ)-catalyzed direct C-H bond activation and lactonization of 2-arylphenols uncovers an attractive strategy to prepare coumarin derivatives with novel chemoselectivity.Motivated by the mechanistic ambiguity(on the origin of the chemoselectivity and the details for lactonization etc.),we conducted a detailed mechanistic study for the rhodium-catalyzed lactonization of 2-arylphenols with density functional theory(DFT)calculations.The results suggest that the reaction occurs via the coordination exchange,C-H bond activation,carboxylation,protonation and lactonization steps.The rate-determining step is the carboxylation,in which CO_(2) favorably inserts into the Rh-C bond(instead of the more nucleophilic Rh-O bond).The protonation step after carboxylation is critical,which makes the subsequent CO_(2)-assisted lactonization feasible.Interestingly,the corresponding pK_(a) value of the base can reasonably predict the reaction energy barrier of the C-H bond activation step.The calculations will provide insights and suggestions for developing and advancing the subsequent C-H bond activation carboxylation reaction.

A mechanistic study on the regioselective Ni-catalyzed methylation–alkenylation of alkyne with AlMe3 and allylic alcohol

The recently reported Ni-catalyzed methylation–allylation of alkynes with allylic alcohols and AlMe3 reagents delivers valuable tetrasubstituted alkene units in a highly regioselective fashion.Motivated by the experimental significance and the mechanistic ambiguity(e.g.the details of C–O bond activation,the function of the Lewis acid AlMe3,etc.),we conducted a detailed mechanistic study using density functional theory(DFT)calculations.The reaction was found to occur via the C–O bond activation of allylic alcohol,allylation of alkyne,transmetalation,reductive elimination and catalyst regeneration steps.AlMe3 could easily react with the allylic alcohol to form a cyclodialuminoxane species bearing two groups of Lewis acid–base interactions.In this regard,the C(allyl)–O bond is remarkably activated,resulting in a relatively facile C–O activation(compared to the typical Lewis-acid mediated reactions).In addition,the Al–Me interaction is a double-edged sword to the methylation step:the cyclodialuminoxane group functions as the methyl resource,while the full dissociation of the Al–Me interaction(via a cis-to-trans isomerization)is a requisite to fully release the methyl group.In this context,the“Me-relay”pathway involving the[Ni]–Me intermediate is found to be more plausible than all other mechanistic possibilities(such as the typical concerted Me-transfer mechanism in previous studies).