Organo/Transition-Metal Combined Catalysis Rejuvenates Both in Asymmetric Synthesis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2415 - 2437

Опубликована: Янв. 20, 2022

Since its advent two decades ago, asymmetric organo/transition-metal combined catalysis (AOMC), including cooperative and relay catalysis, has leveraged redistribution of chemical bonds to build up molecular complexity enantio-differentiation form individual enantiomers with activations from versatile organocatalysts transition-metal complexes. The goal this perspective is provide readers the fundamental attributes AOMC─orthogonality, kinetics, mechanism, selectivity─to understand how an organocatalyst a complex would collaborate enable fruitful new reaction development what are intrinsic pathways unproductive events, such as catalyst self-quenching. In closing, future opportunities AOMC have been directed toward prediction effective combination, introducing enzyme focus on transient radical intermediate, animate area in years come.

Язык: Английский

---

Bimetallic Catalysis in Stereodivergent Synthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(45)

Опубликована: Авг. 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.

Язык: Английский

---

Enantio‐ and Diastereodivergent Synthesis of Spirocycles through Dual‐Metal‐Catalyzed [3+2] Annulation of 2‐Vinyloxiranes with Nucleophilic Dipoles

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(47), С. 24941 - 24949

Опубликована: Сен. 17, 2021

The development of efficient and straightforward methods for obtaining all optically active isomers structurally rigid spirocycles from readily available starting materials is great value in drug discovery chiral ligand development. However, the stereodivergent synthesis bearing multiple stereocenters remains an unsolved challenge owing to steric hindrance ring strain. Herein, we report enantio- diastereodivergent through dual-metal-catalyzed [3+2] annulation oxy π-allyl metallic dipoles with less commonly employed nucleophilic (imino esters). A series spiro compounds a pyrroline olefin were easily synthesized manner (up 19:1 dr, >99 % ee), which showed promise as new type N-olefin ligand. Preliminary mechanistic studies also carried out understand process this bimetallic catalysis.

Язык: Английский

---

Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one

Chem, Год журнала: 2022, Номер 8(7), С. 2011 - 2022

Опубликована: Май 2, 2022

Язык: Английский

---

Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates

Chem, Год журнала: 2022, Номер 8(10), С. 2784 - 2796

Опубликована: Авг. 17, 2022

Язык: Английский

---

Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июнь 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.

Язык: Английский

---

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 3915 - 3925

Опубликована: Фев. 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.

Язык: Английский

---

Synergistic Dual Catalysis in Stereodivergent Synthesis

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 3812 - 3844

Опубликована: Фев. 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.

Язык: Английский

---

Synergistic Pd/Cu-Catalyzed 1,5-Double Chiral Inductions

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9241 - 9251

Опубликована: Март 19, 2024

Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant

Язык: Английский

---

Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(49), С. 20818 - 20827

Опубликована: Дек. 6, 2021

Multicomponent reactions that involve interception of onium ylides through Aldol, Mannich, and Michael addition with corresponding bench-stable acceptors have demonstrated broad applications in synthetic chemistry. However, because the high reactivity transient survival these situ generated intermediates, substitution-type process, especially asymmetric catalytic version, remains hitherto unknown. Herein, a three-component allylation α-diazo carbonyl compounds alcohols allyl carbonates is disclosed by employing ternary cooperative catalysis achiral Pd-complex, Rh2(OAc)4, chiral phosphoric acid CPA. This method represents first example allylic alkylation an SN1-type trapping which involves convergent assembly two active Pd-allyl species, enol derived from ylides, providing expeditious access to α,α-disubstituted ketones good yields excellent enantioselectivity. Combined experimental computational studies shed light on mechanism this novel reaction, including critical role Xantphos ligand origin

Язык: Английский

---