A regioselective [3 + 2] annulation of β,γ-alkynyl-α-ketimino esters with 1,3-dicarbonyls is disclosed. A series of Z-selective dihydrofurans bearing an exocyclic double bond and a quaternary carbon center are accessed without the usage of base. Control and deuterium-labeling experiments have been investigated to probe into the reaction mechanism. The catalyst and base-free nucleophilic addition highlights the transformation.
A TBN-enabled tandem C-H bond oxidation/C-N bond cleavage/[3+2] cycloaddition of 1-nitromethyltetrahydroisoquinolines was realized, constructing a series of multifunctionalized isoxazole and isoxazoline skeletons in the presence of alkynes and alkenes, respectively. Various functional groups were smoothly tolerated, and the mechanistic study revealed that the construction of isoxazole and isoxazoline rings is mediated by the in situ generated nitrile oxides.
The reaction mechanism and the enantioselectivity of the Brønsted acid/base (trans-stilbene diamine, simplified by BAM)-catalyzed CO2 fixation with homoallylic amine have been investigated using density functional theory (DFT) calculations. The proposed mechanism involves the initial activation of the amine by the Brønsted acid, followed by the nucleophilic attack of the amine on CO2 to form a carbamate intermediate. The Brønsted base subsequently deprotonates the carbamate intermediate to form the cyclic carbamate product, regenerating the Brønsted acid catalyst. The C-O cyclization is the enantio-determining step. The hydrogen bond network formed by the catalyst and substrate, similar to an enzyme pocket, plays a key role in stereoselectivity. In addition, the energy decomposition analysis (EDA) confirms that hydrogen bonding is driven by orbital and electrostatic attractions. The more Brønsted basic BAM catalyst (OMe at the quinoline 7-position) exhibits enhanced enantioselectivity.
The selective oxidative cleavage and functionalization of C(OH)-C bonds in tertiary alcohols harbor immense feasibility in organic synthesis and enable the production of high value-added chemicals from renewable biomass. However, it remains a challenge, owing to the inherent kinetic inertness and thermodynamic stability of C(OH)-C bonds and the lack of Cα-H. Taking the huge potential and challenge of C(OH)-C bond activation and functionalization into consideration, herein, we show the first example of an inexpensive bifunctional ferric nitrate catalyst for catalytic direct oxidation of structurally distinct tertiary alcohols to esters with environmentally benign molecular oxygen as an oxidant and MeOH as a solvent, without the assistance of any additives. Detailed mechanistic studies reveal that this tandem catalytic oxidative process is initiated by the synergistic effects of an iron ion and nitrate ion, which serve as Lewis acids for dehydrating and a nitrogen dioxide radical precursor for inducing an oxidative cleavage, respectively.
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