Stereodivergent Construction of Csp3−Csp3Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis DOI

Jingqiang Han,

Rixin Liu,

Zitong Lin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 16, 2022

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation Csp 3 −Csp bonds bearing vicinal stereocenters. Despite many successes that have been achieved in this field, coupling reactions involving stabilized nucleophiles remain challenging because competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system enables diastereodivergent 1,3‐dienes with nucleophile oxindoles. Both syn and anti products, quaternary tertiary stereocenters, could be selectively produced good yields high enantio‐ diastereoselectivities. Non‐covalent activation via chiral ion pair biphasic is crucial success factor achieving diastereodivergence.

Language: Английский

Advances in theE → ZIsomerization of Alkenes Using Small Molecule Photocatalysts DOI
Tomáš Neveselý,

Max Wienhold,

John J. Molloy

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2650 - 2694

Published: Aug. 27, 2021

Geometrical E → Z alkene isomerization is intimately entwined in the historical fabric of organic photochemistry and enjoying a renaissance (Roth et al. Angew. Chem., Int. Ed. Engl. 1989 28, 1193–1207). This consequence fundamental stereochemical importance Z-alkenes, juxtaposed with frustrations thermal reactivity that are rooted microscopic reversibility. Accessing excited state paradigms allow this latter obstacle to be circumnavigated by exploiting subtle differences photophysical behavior substrate product chromophores: provides molecular basis for directionality. While direct irradiation operationally simple, photosensitization via selective energy transfer enables augmentation repertoire include substrates not directly photons. Through sustained innovation, an impressive portfolio tailored small molecule catalysts range triplet energies now widely available facilitate contra-thermodynamic thermo-neutral reactions generate Z-alkene fragments. review intended serve as practical guide covering geometric alkenes enabled catalysis from 2000 2020, logical sequel excellent treatment Dugave Demange (Chem. Rev. 2003 103, 2475–2532). The mechanistic foundations underpinning selectivity discussed together induction models rationales explain counterintuitive directionality these processes which very distinguish product. Implications subsequent stereospecific transformations, application total synthesis, regioselective polyene isomerization, spatiotemporal control pre-existing configuration broader sense discussed.

Language: Английский

Citations

309
Stereodivergent Synthesis of Tertiary Fluoride-Tethered Allenes via Copper and Palladium Dual Catalysis DOI

Shao‐Qian Yang,

Yifan Wang,

Wei-Cheng Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(19), P. 7285 - 7291

Published: May 10, 2021

Herein we describe a protocol for the unprecedented stereodivergent synthesis of tertiary fluoride-tethered allenes bearing stereogenic center and axis via Cu/Pd synergistic catalysis. A broad scope conjugated enynes are coupled with various α-fluoroesters in high yields diastereoselectivities generally >99% ee. In addition, four stereoisomers allene products ensure precise access to corresponding fluorinated hydrofurans novel axial-to-central chirality transfer process.

Language: Английский

Citations

167
Enantio- and Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis DOI
Jiacheng Zhang, Xiaohong Huo, Junzhe Xiao

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12622 - 12632

Published: Aug. 5, 2021

In contrast to the widely explored methods for asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, concurrent construction 1,3-stereogenic centers in an enantio- and diastereoselective manner remains challenge, especially acyclic systems. Herein, we report diastereodivergent 1,3-nonadjacent stereocenters allenyl axial central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic allenylation with racemic allenylic esters. The protocol is suitable wide range substrates including challenging esters less sterically bulky substituents provided chiral products high levels diastereoselectivities (up >20:1 dr >99% ee). Furthermore, several representative transformations involving axial-to-central transfer were conducted, affording useful structural motifs containing nonadjacent manner.

Language: Английский

Citations

165
Bimetallic Catalysis in Stereodivergent Synthesis DOI
Xiaohong Huo, Guanlin Li, Xi Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Aug. 2, 2022

Abstract Bimetallic catalysis has emerged as an efficient strategy for the development of new chemical reactions. Importantly, this also provides a simple and powerful platform stereodivergent synthesis, whereby all possible stereoisomers products bearing two stereocenters can be easily prepared from same set starting materials. In Minireview, allylic substitution, propargylic hydrofunctionalization, annulation based on bimetallic been summarized. It is expected that more catalytic systems will developed applied synthesis valuable molecules.

Language: Английский

Citations

139
Dispersion and Steric Effects on Enantio-/Diastereoselectivities in Synergistic Dual Transition-Metal Catalysis DOI
Bo Li, Hui Xu, Yanfeng Dang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1971 - 1985

Published: Jan. 20, 2022

Comprehensive computational studies were carried out to explore the mechanisms of enantioselective Cu/Pd and stereodivergent Cu/Ir dual-catalytic syntheses α,α-disubstituted α-amino acids (α-AAs). A chiral copper azomethine ylide undergoes facile α-allylation with racemic π-allylpalladium species or stereopure π-allyliridium complex stereoconvergently stereodivergently furnish single/double stereocenters, respectively. Stereoselectivity at α-center is controlled by facial selectivity respect prochiral nucleophile. Despite apparently similar transition-state assemblies, models distortion/interaction analyses disclose versatile modes stereoinduction wherein can face-selectively intercept metal−π-allyl intermediates utilizing attractive dispersion interactions and/or sterically caused distortions. Generation β-stereocenter in system relies on a stereospecifically generated allyliridium electronically branched-to-linear selectivity, while dual yields linear monochiral product due steric factors π–π stacking interactions. The demonstrate molecular level how ligand-encoded information transferred α-/β-sites resulting α-AAs mode regio-/stereoselection altered differences transition-metal-stabilized coupling partners. To facilitate stereoselective catalysis, suite analytical tools extract controlling for asymmetric induction demonstrated.

Language: Английский

Citations

109
Pt1 enhanced C-H activation synergistic with Ptn catalysis for glycerol cascade oxidation to glyceric acid DOI Creative Commons
Zhe An, Zilong Zhang, Zeyu Huang

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 17, 2022

The selective oxidation of glycerol to glyceric acid, an important value-added reaction from polyols, is a typical cascade catalytic process. It still great challenge simultaneously achieve high activity and acid selectivity, suffering either deep C-C cleavage or poor efficiency glyceraldehyde acid. Herein, this work, inspired by nature, proposes synergistic catalysis strategy atomic low-coordinated cluster Pt on well-defined Cu-CuZrOx, which involves enhanced C-H activation Pt1 O-H Ptn in the glyceraldehyde, for C=O followed insertion tandem process revealed be essential (90.0±0.1%) selectivity (80.2±0.2%).

Language: Английский

Citations

86
Pickering emulsion droplet-based biomimetic microreactors for continuous flow cascade reactions DOI Creative Commons
Ming Zhang, Rammile Ettelaie,

Lianlian Dong

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 25, 2022

Abstract A continuous flow cascade of multi-step catalytic reactions is a cutting-edge concept to revolutionize stepwise synthesis yet still challenging in practical applications. Herein, method for one-pot catalysis developed by combining Pickering emulsions with flow. Our involves co-localization different catalytically active sub-compartments within droplets emulsion yielding cell-like microreactors, which can be packed column reactor catalysis. As exemplified two chemo-enzymatic the chiral cyanohydrins and ester, 5 − 420 fold enhancement efficiency as high 99% enantioselectivity were obtained even over period 80 240 h. The compartmentalization effect enriching-reactant properties arising from biomimetic microreactor are theoretically experimentally identified key factors boosting regulating kinetics

Language: Английский

Citations

83
Transition metal nanoparticles as nanocatalysts for Suzuki, Heck and Sonogashira cross-coupling reactions DOI Creative Commons
Muhammad Ashraf,

Muhammad Sohail Ahmad,

Yusuke Inomata

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 476, P. 214928 - 214928

Published: Nov. 11, 2022

Language: Английский

Citations

82
Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates DOI Creative Commons
Qinglong Zhang, Minghui Zhu, Weiwei Zi

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(10), P. 2784 - 2796

Published: Aug. 17, 2022

Language: Английский

Citations

72
Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis DOI
Xin Chang, Xiang Cheng,

Xue‐Tao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 28, 2022

An unprecedented hydroalkylation of racemic allylic alcohols and ketimine esters enabled by Cu/Ru relay catalysis has been developed via merging the ruthenium-catalyzed asymmetric borrowing-hydrogen reaction with a copper-catalyzed Michael addition in one-pot procedure. The current method enables efficient preparation highly functionalized δ-hydroxyesters bearing 1,4-nonadjacent stereocenters good yields high levels diastereoselectivity excellent enantioselectivity under mild conditions. full complement four stereoisomers products could be readily accessed orthogonal permutations two chiral metal catalysts. work highlights power for stereodivergent construction that were otherwise inaccessible.

Language: Английский

Citations

71