Mechanism and origins of stereo- and enantioselectivities of palladium-catalyzed hydroamination of racemic internal allenes via dynamic kinetic resolution: a computational study

The first efficient palladium-catalyzed asymmetric hydrogenation of 2-aryl cyclic ketones has been described through dynamic kinetic resolution under acidic conditions, providing a facile access to chiral trans cycloalkanols.

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Palladium-Catalyzed Enantioselective Arylation of Racemic Ketones to Form Bridged Bicycles via Dynamic Kinetic Resolution

Angewandte Chemie International Edition ◽

10.1002/anie.201804318 ◽

2018 ◽

Vol 57 (26) ◽

pp. 7673-7677 ◽

Cited By ~ 15

Author(s):

Xiaolei Huang ◽

William Ray Jun Jie Oh ◽

Jianrong Steve Zhou

Keyword(s):

Kinetic Resolution ◽

Dynamic Kinetic Resolution ◽

Palladium Catalyzed

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Computational study on palladium-catalyzed alkenylation of remote δ-C(sp3)–H bonds with alkynes: a new understanding of mechanistic insight and origins of site-selectivity

RSC Advances ◽

10.1039/c8ra06077k ◽

2018 ◽

Vol 8 (53) ◽

pp. 30186-30190 ◽

Cited By ~ 1

Author(s):

Hui-Min Yan ◽

Ye Tian ◽

Niu Li ◽

Rong Chang ◽

Zhu-Xia Zhang ◽

...

Keyword(s):

Dft Calculations ◽

Computational Study ◽

Mechanistic Insight ◽

Site Selectivity ◽

Palladium Catalyzed

Palladium-catalyzed alkenylation of δ-C(sp3)–H bonds with alkynes was conducted by DFT calculations, showing that the dimeric Pd2(OAc)4 mechanism reproduces experimental observations well.

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How does the Achiral Base Decide the Stereochemical Outcome in the Dynamic Kinetic Resolution of Sulfinyl Chlorides? A Computational Study

Advanced Synthesis & Catalysis ◽

10.1002/adsc.200700096 ◽

2007 ◽

Vol 349 (13) ◽

pp. 2103-2110 ◽

Cited By ~ 12

Author(s):

David Balcells ◽

Gregori Ujaque ◽

Inmaculada Fernández ◽

Noureddine Khiar ◽

Feliu Maseras

Keyword(s):

Kinetic Resolution ◽

Computational Study ◽

Dynamic Kinetic Resolution

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Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation

Nature Communications ◽

10.1038/s41467-021-27813-4 ◽

2022 ◽

Vol 13 (1) ◽

Author(s):

Ya Lv ◽

Guoyong Luo ◽

Qian Liu ◽

Zhichao Jin ◽

Xinglong Zhang ◽

...

Keyword(s):

Dft Calculations ◽

Kinetic Resolution ◽

Group Formation ◽

Heterocyclic Carbenes ◽

Large Set ◽

Dynamic Kinetic Resolution ◽

Catalytic Activities ◽

Bond Dissociation ◽

Axially Chiral ◽

Chirality Control

AbstractThe applications of axially chiral benzonitriles and their derivatives remain mostly unexplored due to their synthetic difficulties. Here we disclose an unusual strategy for atroposelective access to benzonitriles via formation of the nitrile unit on biaryl scaffolds pre-installed with stereogenic axes in racemic forms. Our method starts with racemic 2-arylbenzaldehydes and sulfonamides as the substrates and N-heterocyclic carbenes as the organocatalysts to afford axially chiral benzonitriles in good to excellent yields and enantioselectivities. DFT calculations suggest that the loss of p-toluenesulfinate group is both the rate-determining and stereo-determining step. The axial chirality is controlled during the bond dissociation and CN group formation. The reaction features a dynamic kinetic resolution process modulated by both covalent and non-covalent catalytic interactions. The axially chiral benzonitriles from our method can be easily converted to a large set of functional molecules that show promising catalytic activities for chemical syntheses and anti-bacterial activities for plant protections.

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