Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes

Chemical Society Reviews, Год журнала: 2020, Номер 49(7), С. 2060 - 2118

Опубликована: Янв. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Язык: Английский

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Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes

ACS Catalysis, Год журнала: 2019, Номер 10(2), С. 1060 - 1076

Опубликована: Дек. 12, 2019

Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin 1,2-disubstituted a single step tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings nucleophiles and 1,3-dienes hydrofunctionalization reactions have quickly emerged as compelling approach to these related compounds. In Perspective, we illustrate how diene hydrofunctionalizations provided avenue complex, highly desirable chemical space that not readily accessed by other technologies. We also aim provide some insight into varying mechanistic pathways nuances myriad help inform future reaction catalyst design.

Язык: Английский

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Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes

Science China Chemistry, Год журнала: 2020, Номер 63(11), С. 1586 - 1600

Опубликована: Сен. 28, 2020

Язык: Английский

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NiH-Catalyzed Functionalization of Remote and Proximal Olefins: New Reactions and Innovative Strategies

Accounts of Chemical Research, Год журнала: 2022, Номер 55(23), С. 3519 - 3536

Опубликована: Ноя. 9, 2022

Transition metal hydride catalyzed functionalization of remote and proximal olefins has many advantages over conventional cross-coupling reactions. It avoids the separate, prior generation stoichiometric amounts organometallic reagents use preformed reagents, which are sometimes hard to access may compromise functional group compatibility. The migratory insertion complexes generated in situ into readily available alkene starting materials, hydrometalation process, provides an attractive straightforward route alkyl intermediates, can undergo a variety sequential In particular, with synergistic combination chain-walking chemistry nickel, NiH-catalyzed undergone particularly intense development past few years. This Account aims chronicle progress made this arena terms activation modes, diverse functionalizations, chemo-, regio-, enantioselectivity.We first provide brief introduction general reaction mechanisms. Taking hydroarylation as example, four oxidation states Ni have allowed us develop two different strategies form final product: Ni(I)-H/X-Ni(II)-H platform that relies on reductants Ni(I/II/III) cycle redox-neutral or FG-Ni(II)-H reacts substrate forms products via Ni(0/II) pathway. We also demonstrate functionalization, including C-C bond-forming reactions more challenging C-N/C-S could be realized. Moreover, employment appropriate chiral ligands successfully realize corresponding asymmetric hydrofunctionalization olefins, hydroalkylation, hydroarylation, hydroalkenylation, hydroalkynylation, hydroamination. Interestingly, enantio-determining step enantioselective hydronickelation, selective oxidative addition, reductive elimination. To hydrofunctionalization, we developed ligand relay catalytic strategy simple ligands, for second coupling. novel design single, possibly structurally complex promote both steps success multicomponent convenient approach gain molecules. Finally, halides used olefin precursors cross-electrophile coupling Applications these discussed. hope will inspire future field overcome key challenges, conceptually new strategies, high-performance systems enhanced reactivity selectivity, cutting-edge catalyst design, further mechanistic studies.

Язык: Английский

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Synergistic Pd/Amine-Catalyzed Stereodivergent Hydroalkylation of 1,3-Dienes with Aldehydes: Reaction Development, Mechanism, and Stereochemical Origins

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(29), С. 10948 - 10962

Опубликована: Июль 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.

Язык: Английский

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NiH-catalyzed asymmetric hydroarylation of N-acyl enamines to chiral benzylamines

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

Опубликована: Янв. 27, 2021

Enantiomerically pure chiral amines and related amide derivatives are privilege motifs in many pharmacologically active molecules. In comparison to the well-established hydroamination, transition metal-catalysed asymmetric hydrofunctionalization of enamines provides a complementary approach for their construction. Here we report NiH-catalysed enantio- regioselective reductive hydroarylation N-acyl enamines, allowing practical access broad range structurally diverse, enantioenriched benzylamines under mild, operationally simple reaction conditions.

Язык: Английский

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Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2919 - 2927

Опубликована: Янв. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Язык: Английский

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Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Язык: Английский

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Enantio‐ and Regioselective NiH‐Catalyzed Reductive Hydroarylation of Vinylarenes with Aryl Iodides

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(48), С. 21530 - 21534

Опубликована: Авг. 28, 2020

Abstract A highly enantio‐ and regioselective hydroarylation process of vinylarenes with aryl halides has been developed using a NiH catalyst new chiral bis imidazoline ligand. broad range structurally diverse, enantioenriched 1,1‐diarylalkanes, structure found in number biologically active molecules, have obtained excellent yields enantioselectivities under extremely mild conditions.

Язык: Английский

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Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(47), С. 18825 - 18835

Опубликована: Ноя. 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

Язык: Английский

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