Palladium‐Catalyzed Asymmetric Intramolecular Reductive Heck Desymmetrization of Cyclopentenes: Access to Chiral Bicyclo[3.2.1]octanes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(9), С. 2884 - 2888

Опубликована: Янв. 21, 2019

Abstract A palladium‐catalyzed asymmetric reductive Heck reaction of unactivated aliphatic alkenes, with eliminable β‐hydrogen atoms, has been realized for the first time. series optically active bicyclo[3.2.1]octanes bearing chiral quaternary and tertiary carbon stereocenters were obtained in good yields excellent enantioselectivities, exhibiting functional‐group tolerance scalability. Moreover, deuterated also high efficiency.

Язык: Английский

---

Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(15), С. 2436 - 2466

Опубликована: Июнь 12, 2023

Abstract Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety biologically pharmacologically relevant natural products, medicinal molecules, functional materials. A major challenge modern synthetic methodology is the development strategically efficient selective construction these from readily available starting Transition‐metal‐catalyzed transformations involving Heck reaction as pivotal step have afforded powerful approach for accessing sophisticated skeletons set easy‐to handle materials, thus highlighting its potential significance streamlining drug discovery process. Over past few decades, significant effort has been devoted to derivatives versatile routes, number direct strategies reported. In this review, latest advances transition‐metal‐catalyzed critical summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki 3) Heck/Heck 4) Heck/Hiyama 5) Heck/Cacchi 6) Heck/C−H bond functionalization reaction.

Язык: Английский

---

Copper‐Catalyzed Asymmetric Annulation Reactions of Carbenes with 2‐Iminyl‐ or 2‐Acyl‐Substituted Phenols: Convenient Access to Enantioenriched 2,3‐Dihydrobenzofurans

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(39), С. 13885 - 13889

Опубликована: Июль 27, 2019

We have developed a method for the highly diastereo- and enantioselective construction of 2,3-dihydrobenzofurans bearing tetrasubstituted carbon stereocenters by means annulation reactions between carbenes 2-iminyl- or 2-acyl-substituted phenols through catalysis readily accessible copper(I)/bisoxazoline catalysts under mild conditions. These feature unique mechanism in which copper catalyst serves dual function: first it reacts with diazo compound to generate metal carbene, second, upon formation an oxonium ylide, acts as Lewis acid activate imine ketone cyclization.

Язык: Английский

---

Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Angewandte Chemie, Год журнала: 2019, Номер 131(20), С. 6794 - 6798

Опубликована: Март 20, 2019

Abstract Reported is an asymmetric reductive dicarbofunctionalization of unactivated alkenes. Under the catalysis a Ni/BOX system, various aryl bromides, incorporating pendant olefinic unit, were successfully reacted with array primary alkyl bromides in presence Zn as reductant, furnishing series benzene‐fused cyclic compounds bearing quaternary stereocenter high enantioselectivities. Notably, this reaction avoids use pregenerated organometallics and demonstrates tolerance sensitive functionalities. The preliminary mechanistic investigations reveal that Ni‐catalyzed proceeds cascade consisting migratory insertion cross‐coupling nickel(I)‐mediated intramolecular 5‐ exo cyclization enantiodetermining step.

Язык: Английский

---

Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction

Angewandte Chemie, Год журнала: 2019, Номер 131(41), С. 14795 - 14801

Опубликована: Авг. 17, 2019

Abstract A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example intramolecular cyclization/cross‐coupling olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to number chiral compounds, such as dihydrobenzofurans, indolines, chromanes, indanes bearing quaternary stereocenter, in good yields excellent enantioselectivities. The practicality this validated modification biologically complex molecules peptides, piperitol, CB2 receptor agonists, etc. Moreover, synthesis two enantiomers can be easily realized simple change order steps sequence.

Язык: Английский

---

Enantioselective Intermolecular Heck and Reductive Heck Reactions of Aryl Triflates, Mesylates, and Tosylates Catalyzed by Nickel

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(6), С. 2828 - 2832

Опубликована: Ноя. 3, 2020

Nickel-catalyzed intermolecular Heck reaction of cycloalkenes proceeds well with aryl triflates, mesylates and tosylates in excellent enantiomeric ratios. The asymmetric reductive also works a 2-cyclopentenone ketal, which is equivalent to conjugate arylation the enone itself.

Язык: Английский

---

Palladium/TY‐Phos‐Catalyzed Asymmetric Intermolecular α‐Arylation of Aldehydes with Aryl Bromides

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(34), С. 18542 - 18546

Опубликована: Июнь 9, 2021

Abstract Despite much progress has been made in the asymmetric α‐arylation reactions of cyclic ketones, lactones and lactams, enantioselective acyclic carbonyl compounds lagged behind due to situ generated Z/E‐enolate intermediates leading opposite enantiomers. Especially, aldehydes is a long‐standing challenge, because highest activity among various competitive side reactions. Herein we reported an efficient Pd‐catalyzed intermolecular reaction α‐alkyl‐α‐aryl disubstituted with aryl bromides, which provides rapid access chiral bearing α‐all‐carbon quaternary stereocenter moderate good yields er most cases. In addition, pair enantiomers could be easily prepared use same ligand by exchanging groups aldehyde bromide.

Язык: Английский

---

Palladium/PC‐Phos‐Catalyzed Asymmetric Heck/Tsuji–Trost Reactions of Amino‐Tethered 1,3‐Cyclohexadiene with Aryl and Alkenyl Halides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Ноя. 1, 2022

Chiral perhydroindoles are found in a number of natural products and biologically active compounds. Therefore, the development new asymmetric methodology for rapid access to this core is high importance. Herein, we reported highly regio- diastereo-selective palladium/PC-Phos-catalyzed Heck/Tsuji-Trost reactions readily available amino tethered 1,3-cyclohexadienes with aryl alkenyl halides, delivering various functionalized chiral hexahydroindoles good yields enantioselectivity. The application reaction concise synthesis (-)-α-Lycorane was demonstrated. DFT computation results indicate that difference ΔEdis two migration insertion transition states determines enantioselectivity reaction.

Язык: Английский

---

Pd‐Catalyzed Enantioselective Ring Opening/Cross‐Coupling and Cyclopropanation of Cyclobutanones

Angewandte Chemie, Год журнала: 2018, Номер 131(3), С. 907 - 911

Опубликована: Ноя. 20, 2018

Abstract A palladium‐catalyzed enantioselective sequential ring‐opening/cross‐coupling of cyclobutanones is disclosed that provides chiral indanones bearing C3‐quaternary stereocenters. The reaction process involves nucleophilic addition and aryl halides, β‐carbon elimination, intermolecular trapping a transient σ‐alkylpalladium complex with boronic acids. Alternatively, an intramolecular cyclopropanation realized through C−H bond functionalization in the absence external coupling reagents, affording cyclopropane‐fused‐indanones good yields enantioselectivity.

Язык: Английский

---

Asymmetric Synthesis of Enantioenriched 2‐Aryl‐2,3‐Dihydrobenzofurans by a Lewis Acid Catalyzed Cyclopropanation/Intramolecular Rearrangement Sequence

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(38), С. 13427 - 13432

Опубликована: Июль 16, 2019

A cyclopropanation/intramolecular rearrangement initiated by the Michael addition of in situ generated ortho-quinone methides (o-QMs) has been developed for enantioselective synthesis 2-aryl-2,3-dihydrobenzofurans containing two consecutive stereogenic centers, including a quaternary carbon atom. In presence chiral oxazaborolidinium ion catalyst, reaction proceeded excellent yields (up to 95 %) with stereoselectivity >99 ee, up >20:1 d.r.).

Язык: Английский

---