Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

The Chemical Record, Год журнала: 2018, Номер 18(9), С. 1314 - 1340

Опубликована: Март 8, 2018

Abstract Transition metal (TM)‐catalyzed difunctionalization of unactivated olefins with two carbon‐based entities is a powerful method to construct complex molecular architectures rapidly from simple and readily available feedstock chemicals. While dicarbofunctionalization has long history typically the use either carbon monoxide intercept C(sp 3 )‐[M] (alkyl‐TM) species or substrates lacking in β‐hydrogen (β‐Hs), development this class reaction still remains seriously limited due complications β‐H elimination arising situ‐generated intermediates. Over years, different approaches have been harnessed suppress elimination, which led various types olefin reactions even that generate intermediates bearing β‐Hs wide range electrophiles nucleophiles. In review, these developments will be discussed both through lens historical perspectives as well strategies scrutinized over years address issue elimination. However, review article by no means designed exhaustive field, merely presented provide readers an overview key developments.

Язык: Английский

---

Nickel-Catalyzed Reductive Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(20), С. 6835 - 6838

Опубликована: Май 10, 2017

An intermolecular, three-component reductive dicarbofunctionalization of alkenes is presented here. The combination Ni catalysis with TDAE as final reductant enables the direct formation Csp3–Csp3 and Csp3–Csp2 bonds across a variety π-systems using two different electrophiles that are sequentially activated exquisite selectivity under mild reaction conditions.

Язык: Английский

---

Ni-Catalyzed Enantioselective Reductive Diarylation of Activated Alkenes by Domino Cyclization/Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(39), С. 12364 - 12368

Опубликована: Сен. 20, 2018

A Ni-catalyzed enantioselective reductive diarylation of activated alkenes by domino cyclizative/cross-coupling two aryl bromides is developed. This reaction proceeds under very mild conditions and shows broad substrate scope, without requiring the use preformed organometallic reagents. Moreover, this approach provides direct access to various bis-heterocycles bearing all-carbon quaternary centers in synthetically useful yields (up 81%) with excellent enantioselectivity (>30 examples, 90–99% ee).

Язык: Английский

---

Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(31), С. 10657 - 10660

Опубликована: Июль 24, 2017

A nickel-catalyzed conjunctive cross-coupling between non-conjugated alkenes, aryl iodides, and alkylzinc reagents is reported. Excellent regiocontrol achieved utilizing an 8-aminoquinoline directing group that can be readily cleaved to unmask net β,γ-dicarbofunctionalized carboxylic acid products. Under optimized conditions, both terminal internal alkene substrates provided the corresponding alkyl/aryl difunctionalized products in moderate excellent yields. The methodology developed herein represents first three-component 1,2-dicarbofunctionalization of alkenes involving a C(sp3)–C(sp3) reductive elimination step.

Язык: Английский

---

Nickel‐Catalyzed Asymmetric Reductive Diarylation of Vinylarenes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(10), С. 3198 - 3202

Опубликована: Янв. 25, 2019

Abstract A nickel‐catalyzed asymmetric diarylation reaction of vinylarenes enables the preparation chiral α,α,β‐triarylated ethane scaffolds, which exist in a number biologically active molecules. The use reducing conditions with aryl bromides as coupling partners obviates need for stoichiometric organometallic reagents and tolerates broad range functional groups. application an N ‐oxyl radical ligand to nickel catalyst represents novel approach facilitate cross‐coupling reactions.

Язык: Английский

---

Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes

Chemistry - An Asian Journal, Год журнала: 2018, Номер 13(17), С. 2277 - 2291

Опубликована: Июнь 13, 2018

Abstract Three‐component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten synthetic path. Recently, transition‐metal catalysis has been applied difunctionalization of alkenes remarkable progress achieved to facilitate construction a wide range functional molecules with high atom‐ step‐economic efficiency. This Focus Review highlights recent advances this field.

Язык: Английский

---

Asymmetric Ni-Catalyzed Radical Relayed Reductive Coupling

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(31), С. 13515 - 13522

Опубликована: Июнь 29, 2020

Alkene dicarbofunctionalizations enable the streamlined construction of aliphatic structures and have thus been subject intense research efforts. Despite significant progress, catalytic asymmetric variants remain scarce. Inspired by advantages reductive cross-coupling approaches, we present here a highly efficient intermolecular Ni-catalyzed dicarbofunctionalization alkenes. Two distinct readily available electrophiles, namely, Csp2- Csp3-halides, are added simultaneously across variety olefins (vinyl amides, vinyl boranes, phosphonates) at room temperature in regio- enantioselective manner. The reaction, devoid sensitive organometallic reagents, takes advantage an situ generated chiral alkyl Ni(III)-intermediate to ensure stereodefined outcome Csp3–Csp2 bond-forming reaction. An (l)-(+)-isoleucine bisoxazoline ligand presence coordinating sites on alkene key for successful these "asymmetric radical relayed couplings" (ARRRCs). Further, multiple transformations amides obtained this process showcase potential new methodology straightforward assembly building blocks such as primary secondary amines oxazolines, highlighting its synthetic utility.

Язык: Английский

---

Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Год журнала: 2020, Номер 431, С. 213683 - 213683

Опубликована: Дек. 9, 2020

Язык: Английский

---

Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities

Chemical Science, Год журнала: 2017, Номер 9(3), С. 600 - 607

Опубликована: Окт. 26, 2017

We present herein a nickel-catalyzed dicarbofunctionalization of alkenes using readily available organoboronic acids and organic halides in three-component fashion.

Язык: Английский

---

Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(31), С. 10653 - 10656

Опубликована: Июль 24, 2017

We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes by intercepting Heck C(sp3)–NiX intermediates with arylzinc reagents. This approach utilizes readily removable imine as coordinating group that plays dual role oxidative addition species derived from aryl halides and triflates to promote carbometalation stabilizing the transient metallacycles suppress β-hydride elimination facilitate transmetalation/reductive steps. method affords diversely substituted 1,1,2-triarylethyl products occur structural motifs various natural products.

Язык: Английский

---