Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(43), С. 17989 - 17994

Опубликована: Окт. 20, 2021

Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- stereoselectively, resultant palladium(II) species undergo cascade Suzuki with organoboronic reagents. The substrate scope is substantial for asymmetric three-component process, enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in modular cis-difunctionalized manner. Control experiments density functional theory (DFT) calculations support idea acts as π-Lewis base catalyst by chemoselectively forming η2-complexes moiety 1,3-enynes, thus increasing nucleophilicity alkyne group based on principle vinylogy, to attack imines enantioselectively. preferable formation aza-palladacyclopentene intermediates, via 90° single bond rotation from π-allyl complex, guarantees formal cis-carbopalladation group. In addition, palladium(0)-catalyzed enantioselective reductive 1,3-enyne imine realized using formic acid hydrogen transfer reagent.

Язык: Английский

---

Simultaneous construction of axial and planar chirality by gold/TY-Phos-catalyzed asymmetric hydroarylation

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июль 29, 2021

Abstract The simultaneous construction of two different chiralities via a simple operation poses considerable challenge. Herein cationic gold-catalyzed asymmetric hydroarylation ortho-alkynylaryl ferrocenes derivatives is developed, which enable the axial and planar chirality. here identified TY-Phos derived gold complex responsible for high yield, good diastereoselectivity (>20:1 dr), enantioselectivities (up to 99% ee) mild conditions. catalyst system also shows potential application in synthesis chiral biaryl compounds. cause enantioselectivity this investigated with density functional theory caculation.

Язык: Английский

---

Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji–Trost of Benzotriazoles with 1,3-Dienes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 13010 - 13015

Опубликована: Авг. 17, 2021

The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of benzotriazole with unsaturated hydrocarbons been explored so far, because the ring-opening generate α-imino metal carbenoid species is thermodynamically unfavorable process. We herein report an efficient benzotriazoles cyclic and acyclic 1,3-dienes enabled by Pd sulfonamide phosphine ligand. A variety substituted hexahydrocarbazoles indolines were delivered in good yields high ee values. Interestingly, pair enantiomers could be obtained use Xu1 PC2 same absolute configuration. synthetic utilities optically active also showcased.

Язык: Английский

---

Organocatalytic Asymmetric Dearomatization Reaction for the Synthesis of Axial Chiral Allene-Derived Naphthalenones Bearing Quaternary Stereocenters

Organic Letters, Год журнала: 2021, Номер 23(17), С. 6606 - 6611

Опубликована: Авг. 13, 2021

The highly regio-, diastereo-, and enantioselective dearomatization reaction of 1-substituted 2-naphthols β,γ-alkynyl-α-imino esters with complete atom economy is disclosed via chiral phosphoric acid catalysis. This protocol provides facile efficient access to asymmetric construction a broad range axially allene-derived naphthalenones bearing quaternary stereocenters in good yields high diastereoselectivities enantioselectivities.

Язык: Английский

---

Recent advances in the metal-catalyzed asymmetric synthesis of chiral allenes

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(18), С. 5053 - 5073

Опубликована: Янв. 1, 2022

Recent advances in the metal-catalyzed asymmetric synthesis of chiral allenes are summarized. This review is categorized based on starting material, including alkynes, racemic allenes, and conjugated dienes.

Язык: Английский

---

Pd/Xu-Phos-catalyzed asymmetric elimination of fully substituted enol triflates into axially chiral trisubstituted allenes

Science Advances, Год журнала: 2023, Номер 9(11)

Опубликована: Март 17, 2023

The β-H elimination, as one of the most important elementary reactions in transition metal chemistry, is a key step quenching carbon-palladium bond for Heck reaction. However, elimination alkenyl palladium species leading to allene an energetically unfavored process, and therefore, it has been long-standing challenge control this process via enantioselective manner. We developed concise efficient methodology construct trisubstituted chiral allenes from stereodefined fully substituted enol triflates by under mild conditions. identified Xu-Phos play crucial role chemoselectivity enantioselectivity. Multiple linear regression analysis shows steric effect on DFT computation results allow us propose intramolecular base (-OAc)-assisted deprotonation mechanism progress. Distortion-interaction energy decomposition indicate that difference electrostatic (Eelec) two base-assisted states dominates stereoselectivity.

Язык: Английский

---

Enantioselective Synthesis of Dihydropyrazoles by Palladium/Xu‐Phos‐Catalyzed Alleneamination of β,γ‐Unsaturated Hydrazones with Propargylic Acetates

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Март 10, 2023

The palladium-catalyzed asymmetric carboamination reaction is one of the most significant transformations in organic chemistry. Herein, we report first alleneamination β,γ-unsaturated hydrazones with propargylic acetates. This protocol enables efficient installation various multisubstituted allene groups onto dihydropyrazoles good yields excellent enantioselectivities. chiral sulfinamide phosphine ligand Xu-5 exhibits highly stereoselective control this protocol. salient features include readily available starting materials, a broad substrate scope, an easy scale-up, mild conditions and versatile transformations.

Язык: Английский

---

Novel Stereo‐Induction Pattern in Pudovik Addition/Phospha‐Brook Rearrangement Towards Chiral Trisubstituted Allenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 23, 2024

Abstract Despite the significance of chiral allene skeletons in catalysis, organic synthesis and medicinal chemistry et al., there is a scarcity reports on axially allenyl phosphorus compounds. Here, we disclosed an efficient straightforward cascade reaction between ethynyl ketones phosphine oxides, resulting broad array trisubstituted allenes incorporating moiety high yields with excellent stereoselectivities facilitated by peptide‐mimic phosphonium salt (PPS) Additionally, comprehensive series mechanistic experiments have been conducted to elucidate that this proceeds via asymmetric Pudovik addition followed subsequent phospha ‐Brook rearrangement occurs concomitantly kinetic resolution, representing stereospecific protonation process facilitating central‐to‐axial chirality transfer manner. We anticipate our research will pave way for promising exploration novel stereo‐induction pattern addition/ reaction.

Язык: Английский

---

Palladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 18, 2024

Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial. However, originate chirality from the distorted structure around heptagon-containing polyarenes largely overlooked, all-carbon remains a challenge. Herein, we present highly route fabricating all carbon via palladium-catalyzed carbene-based cross-coupling benzyl bromides N-arylsulfonylhydrazones. A wide range nonplanar, saddle-shaped tribenzocycloheptene derivatives are efficiently prepared in high yields with excellent enantioselectivities using this approach. In addition, stereochemical stability experiments show that these have inversion barriers.

Язык: Английский

---

Enantioselective synthesis of inherently chiral 9-benzylidene-9H-tribenzo[a,c,e][7]annulene and its application as a ligand platform

Chem Catalysis, Год журнала: 2024, Номер 4(3), С. 100904 - 100904

Опубликована: Янв. 31, 2024

Язык: Английский

---