Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO2 DOI
Xiao‐Wang Chen, Lei Zhu, Yong‐Yuan Gui

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(47), P. 18825 - 18835

Published: Nov. 8, 2019

The catalytic asymmetric functionalization of readily available 1,3-dienes is highly important, but current examples are mostly limited to the construction tertiary chiral centers. generation acyclic products containing all-carbon quaternary stereocenters from substituted represents a more challenging, desirable, synthetic process for which there very few examples. Herein, we report selective copper-catalyzed via with CO2. A variety 1,1-disubstituted 1,3-dienes, as well 1,3,5-triene, undergo reductive hydroxymethylation high chemo-, regio-, E/Z-, and enantioselectivities. reported method features good functional group tolerance, scaled up at least 5 mmol starting diene, generates that useful building blocks further derivatization. Systemic mechanistic investigations using density theory calculations were performed provided first theoretical investigation an transformation involving These computational results indicate 1,2-hydrocupration 1,3-diene proceeds π-facial selectivity generate (S)-allylcopper intermediate, induces chirality carbon center in final product. 1,4-addition internal allylcopper complex, differs previous reports terminal allylmetallic intermediates, CO2 kinetically determines E/Z- regioselectivity. rapid reduction copper carboxylate intermediate corresponding silyl-ether presence Me(MeO)2SiH provides exergonic impetus leads chemoselective rather than carboxylation. provide new insights guiding development C-C bond formations

Language: Английский

Synergistic Pd/Amine-Catalyzed Stereodivergent Hydroalkylation of 1,3-Dienes with Aldehydes: Reaction Development, Mechanism, and Stereochemical Origins DOI
Hongfa Wang, Ruiyuan Zhang, Qinglong Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(29), P. 10948 - 10962

Published: July 15, 2021

Metal-hydride-catalyzed hydroalkylation of 1,3-dienes with enolizable carbonyl compounds is an atom- and step-economical method for preparing chiral molecules allylic stereocenters. Although high diastereo- enantioselectivities have been achieved many coupling partners, aldehydes not yet used this purpose because they are less stable than other under basic conditions the potential to rapidly epimerize at α-position. Moreover, stereodivergent reactions access complementary diastereomers vicinal stereocenters challenging. Herein, we describe a synergistic palladium/amine catalyst system that allowed us achieve first aldehydes. By choosing appropriate combination palladium amine catalysts, could obtain either syn or anti products, therefore provides highly enantioselective α,β-vicinal Density functional theory calculations revealed mechanism involving PdH formation migratory insertion into alkene, followed by C–C bond formation. The origin stereoselectivities was investigated means distortion/interaction analysis.

Language: Английский

Citations

120
Stereodivergent Synthesis of Enantioenriched γ‐Butyrolactones Bearing Two Vicinal Stereocenters Enabled by Synergistic Copper and Iridium Catalysis DOI

Lu Xiao,

Liang Wei, Chun‐Jiang Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(47), P. 24930 - 24940

Published: Oct. 11, 2021

By virtue of a fundamentally new reaction model azomethine ylide serving as two-atom synthon, we present the first example stereodivergent preparation γ-butyrolactones via synergistic Cu/Ir-catalyzed asymmetric cascade allylation/lactonization, and all four stereoisomers bearing two vicinal stereocenters are accessible with excellent diastereoselective enantioselective control. The chiral IrIII -π-allyl intermediate was separated characterized to understand origin regio- stereoselectivity initial C-C bond formation process. Control experiments shed some light on catalyst/substrate catalyst/catalyst interactions in this dual catalytic system rationalize related kinetic/dynamic kinetic resolution process different catalyst combinations. enantioenriched γ-butyrolactone products were converted into an array structurally complex molecules organocatalysts that otherwise inaccessible.

Language: Английский

Citations

115
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
Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one DOI Creative Commons
Yang Xu,

Hongkai Wang,

Zhuang Yang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(7), P. 2011 - 2022

Published: May 2, 2022

Language: Английский

Citations

87
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
Stereodivergent Synthesis of Allenes with α,β‐Adjacent Central Chiralities Empowered by Synergistic Pd/Cu Catalysis DOI
Ling Zhao, Yicong Luo, Junzhe Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(9)

Published: Jan. 3, 2023

The stereodivergent synthesis of allene compounds bearing α,β-adjacent central chiralities has been realized via the Pd/Cu-catalyzed dynamic kinetic asymmetric alkylation racemic allenylic esters. matched reactivity bimetallic catalytic system enables challenging reaction aryl-substituted acetates with sterically crowded aldimine esters smoothly under mild conditions. Various chiral non-natural amino acids a terminal allenyl group are easily synthesized in high yields and excellent diastereo- enantioselectivities (up to >20 : 1 dr, >99 % ee). Importantly, all four stereoisomers product can be readily accessed by switching configurations two metal catalysts. Furthermore, easy interconversion between uncommon η3 -butadienyl palladium intermediate featuring weak C=C/Pd coordination bond stable Csp2 -Pd is beneficial for transformation process (DyKAT).

Language: Английский

Citations

44
Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes DOI

Shao‐Qian Yang,

Aijun Han, Yang Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3915 - 3925

Published: Feb. 10, 2023

The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit synthetic chemistry. Abundant applications free enantioenriched allyl alcohol and hydroxylamine motifs have made the asymmetric hydration hydroaminoxylation conjugated dienes from water hydroxylamine, respectively, intriguing efficient routes that have, however, unachievable thus far. A fundamental challenge is failure to realize transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization dienes. Here, we perform comprehensive study toward stereoselective formal by synthesizing set new P,N-ligands identifying an aryl-derived oxime surrogate for both hydroxylamine. Asymmetric hydroalkoxylation with also elucidated. Furthermore, versatile derivatizations following provide indirect but concise hydrophenoxylation, hydrofluoroalkoxylation, hydrocarboxylation unreported Finally, ligand-to-ligand hydrogen transfer process proposed based on results preliminary mechanistic experiments.

Language: Английский

Citations

44
Dual-Catalyzed Stereodivergent Electrooxidative Homocoupling of Benzoxazolyl Acetate DOI
Jiayin Zhang,

Wangjie Zhu,

Ziting Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1522 - 1531

Published: Jan. 3, 2024

The development of a reliable strategy for stereodivergent radical reactions that allows convenient access to all stereoisomers homocoupling adducts with multiple stereogenic centers remains an unmet goal in organic synthesis. Herein, we describe dual-catalyzed electrooxidative C(sp3)–H/C(sp3)–H complete absolute and relative stereocontrol the synthesis molecules contiguous quaternary stereocenters general predictable manner. reaction is achieved by synergistically utilizing two distinct chiral catalysts convert identical racemic substrates into inherently distinctive reactive intermediates, dictate enantioselective addition, allow full complement stereoisomeric products via simple catalyst permutation. successful execution dual-electrocatalytic programmed activation provides significant conceptual advantage will serve as useful foundation further research cooperative stereocontrolled transformations diversity-oriented

Language: Английский

Citations

35
Synergistic Dual Catalysis in Stereodivergent Synthesis DOI
Liang Wei, Cong Fu,

Zuo-Fei Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3812 - 3844

Published: Feb. 23, 2024

Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, their relative absolute configuration often determine physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only great significance, but also highly challenging since the formation one diastereomers inherently preferred most asymmetric reactions. dual catalysis, introduced 2013 by Carreira group, perfectly catered to all requirements for full stereoselectivity control given reactions two catalysts are utilized a synergistic way act independently, has now been arguably efficient strategy realize stereodivergent synthesis. This comprehensive review presents an overview development enabled catalysis past ten years, providing readers fundamental attributes as well ability, scope, mechanism, limitations this strategy.

Language: Английский

Citations

31