Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Huang, Yuan; Ma, Chao; Liu, Song; Yang, Li‐Cheng; Lan, Yu; Zhao, Yu

doi:10.1016/j.chempr.2021.02.018

Cited by 28 publications

(8 citation statements)

References 42 publications

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“…It should be noted that the amide oxygen assisted the abstraction of the alkyne terminal proton in the transition state TS3. The rate limiting step was the coupling step with a reasonable energy barrier of 26.1 kcal/mol, which is consistent with previous DFT studies on the coupling reactions catalyzed by Ni and Cu 42 . The mechanistic postulation (Fig.…”

Section: Synthetic Utility Of the Annulation/alkynylation Methodsupporting

confidence: 89%

Nickel-catalyzed enantioselective annulation/alkynylation and Sonogashira reaction to form C(sp3)-C(sp) and C(sp2)-C(sp) bonds, respectively

Chen

Liao

Tian

et al. 2021

Preprint

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While traditional Sonogashira reaction requires a palladium catalyst and a copper co-catalyst, some recent variants were reported being promoted by single transition metals. Here we report a single nickel-catalyzed tandem Heck-Sonogashira annulation/alkynylation for enantioselectively constructing C(sp3)-C(sp) bond. In addition, using the same catalytic system, Sonogashira C(sp2)-C(sp) cross-coupling has also been achieved. The alkynylations described in this report are important for the three reasons: 1. C(sp3)/(sp2)-C(sp) bonds exist in many bioactive natural products and drug molecules as well as their key synthetic intermediates; 2. There was no precedent for single nickel-catalyzed Sonogashira reaction owing to the difficulties caused by strong coordination of nickel to the triple bond to inactivate the catalyst; 3. Isolation and characterization of single-crystal structure of a resting state intermediate, di-phosphine chelated σ-alkyl-NiII-I complex, which provided crucial evidence to support the mechanistic postulation and guided DFT calculations.

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Section: Synthetic Utility Of the Annulation/alkynylation Methodsupporting

confidence: 89%

Nickel-catalyzed enantioselective annulation/alkynylation and Sonogashira reaction to form C(sp3)-C(sp) and C(sp2)-C(sp) bonds, respectively

Chen

Liao

Tian

et al. 2021

Preprint

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“…The Zhao group developed a strategy for the stereospecific allylic alkylations under nickel and copper catalysis using vinyl epoxides/VCCs and terminal alkynes as starting materials (Scheme 10). 17 Under the same reaction conditions, variation of ligands led to the formation of either bimolecular allyl acetylene or trimolecular dienyne compounds. DFT calculations provide a rationale for the divergent reactivities.…”

Section: New Reactions Between Vccs and Nucleophilesmentioning

confidence: 99%

Recent Advances in Decarboxylative Conversions of Cyclic Carbonates and Beyond

Yan¹,

Guo²

2021

Synthesis

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Functionalized cyclic organic carbonates have emerged as valuable building blocks for the construction of interesting and useful molecules upon decarboxylation under transition metal catalysis in recent years. With suitable catalytic system, the development of chemo-, regio-, stereo- and enantioselective methods for the synthesis of useful and interesting compounds has advanced greatly. On the basis of previous research work on this topic, this short review will highlight the synthetic potential of cyclic carbonates under transition metal catalysis in last two years. 1 Introduction 2 Transition metal catalyzed decarboxylation of vinyl cyclic carbonates 3 Zwitterionic enolate chemistry based on transition metal catalysis 4 Decarboxylation of alkynyl cyclic carbonates and dioxazolones 5 Conclusions and perspectives

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“…Zhao's recent research offers a compelling illustration of how ligand coordination can exert a significant influence on the reactivity within a catalytic system. 88 The research group reported a Ni/Cu cocatalyzed divergent allylic alkylation of vinyl epoxides and aziridines using alkynes, as shown in Figure 27A. When employing a hemilabile P,N-ligand, Me-PHOX (L39), a dienyne formation occurred as a three-component reaction to afford 43.…”

Section: Ni(0)-catalyzed Reactions Of Alkynesmentioning

confidence: 99%

P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

Bae,

Cho

2023

ACS Catal.

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Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic and steric tunability. Their hemilabile nature, coupled with the ability to modulate both electronic and steric properties through the choice of donor atoms and substituents, has expanded the horizons of chemical transformations. This Review focuses on Nicatalyzed cross-coupling reactions mediated by P,N ligands. The asymmetrical nature of P,N ligands, with each donor atom playing a specific role in the catalytic cycle, offers control, stability, and unique regioselectivity in catalytic processes. In particular, the Ni/P,N-catalytic system exhibits remarkable reactivity with πsubstrates including alkenes, alkynes, and allenes. A thorough mechanistic understanding of these processes offers insights into the trends and future directions in Ni/P,N-catalyzed cross-coupling reactions.

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Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Cited by 28 publications

References 42 publications

Nickel-catalyzed enantioselective annulation/alkynylation and Sonogashira reaction to form C(sp3)-C(sp) and C(sp2)-C(sp) bonds, respectively

Nickel-catalyzed enantioselective annulation/alkynylation and Sonogashira reaction to form C(sp3)-C(sp) and C(sp2)-C(sp) bonds, respectively

Recent Advances in Decarboxylative Conversions of Cyclic Carbonates and Beyond

P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

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