Parallel Kinetic Resolution through Palladium-Catalyzed Enantioselective Cycloimidoylation: En Route to Divergent <i>N</i>-Heterocycles Bearing a Quaternary Stereogenic Center

Wang, Xilong; Luo, Yu; Li, Jing; Wang, Chaoqin; Liu, Qianwen; He, Yimiao; Zhu, Qiang

doi:10.1021/acscatal.2c04941

Cited by 7 publications

(2 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5,6 Particularly, five-and six-membered N-heterocycles are notable for their structural diversity and associated applications. 7,8 Despite their significance, many existing synthesis methods for these N-heterocycles rely on transition metal catalysis, 6−8 presenting economic, environmental, and operational challenges. Consequently, sustainable, transitionmetal-free synthesis methodologies have emerged.…”

Section: ■ Introductionmentioning

confidence: 99%

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

Zou,

Sun,

Hong

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

This study elucidates the mechanisms and principles governing chemoselectivity in synthesizing two distinct Nheterocycles, benzimidazole thiazine and benzothiazole imidazole, through BF 3 •OEt 2 -catalyzed cyclization reactions of propargyl alcohols with benzimidazole thiols. Employing density functional theory calculations, we highlight the crucial role of fluorine source in influencing chemoselectivity. In DCM, BF 3 , as the catalytic center, coordinates with propargyl alcohol's hydroxyl group to form a precursor. Conversely, in DMF, [BF 2 •DMF] + , formed from DMF and BF 3 •OEt 2 , acts as the catalytic center, activating the propargyl alcohol's hydroxyl group. The mechanisms in both solvents involve sequential steps: B−O bond formation, C−O bond cleavage, S− C bond formation, hydrogen atom transfer (HAT), cyclization, and deprotonation. A notable difference is the HAT process: in DCM, it follows a 1,5-HAT process, while in DMF, BF 4 − formation from DMF and BF 3 •OEt 2 provides a fluorine source and introduces steric hindrance, favoring a 1,6-HAT process and leading to unique chemoselectivity. This pioneering research showcases the impact of DMF on cyclization reactions, offering valuable insights for comprehending and designing reactions driven by fluorine sources. Crucially, our results propose an innovative reaction mechanism featuring lower potential energy surfaces, enhancing our understanding of the intricate interplay among reactants, catalysts, and solvents.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

Zou,

Sun,

Hong

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Therefore, in sharp contrast to the traditional resolution, much less successful examples have been reported on PKR. 15 Most of the studies developed so far in this field involve metal catalysis, 16 whilst examples of catalytic PKRs in enantioselective organocatalysis are, however, very limited. 10,17…”

Section: Introductionmentioning

confidence: 99%

Parallel kinetic resolution of aziridines via chiral phosphoric acid-catalyzed apparent hydrolytic ring-opening

Liu,

Du,

et al. 2023

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Chemodivergent Parallel Kinetic Resolution of Paracyclophanes: Enantiomer Fishing with Different Substrates

Liu,

Teng,

Zhang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

An unprecedented chemodivergent strategy for parallel kinetic resolution (PKR) is disclosed through which two planar chiral products bearing different structures were simultaneously afforded with opposite stereoselectivities. Two achiral esters are activated by one single chiral N‐heterocyclic carbene (NHC) catalyst to react with the different enantiomers of the racemic imine substrate in a parallel fashion. Two products bearing distinct structures and opposite stereoselectivities are respectively afforded from the same reaction system in good to excellent yields, enantio‐ and diastereoselectivities. Control experiments and kinetic studies are carried out to probe the kinetic and dynamic properties during the reaction progress. The planar chiral pyridine and lactam products show interesting applications in both asymmetric synthesis and pesticide development.

show abstract

Parallel Kinetic Resolution through Palladium-Catalyzed Enantioselective Cycloimidoylation: En Route to Divergent N-Heterocycles Bearing a Quaternary Stereogenic Center

Cited by 7 publications

References 46 publications

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

Parallel kinetic resolution of aziridines via chiral phosphoric acid-catalyzed apparent hydrolytic ring-opening

Chemodivergent Parallel Kinetic Resolution of Paracyclophanes: Enantiomer Fishing with Different Substrates

Contact Info

Product

Resources

About