Asymmetric Reductive Dicarbofunctionalization of Alkenes via Nickel Catalysis

Anthony, David R.; Diao, Tianning

doi:10.1055/s-0040-1707900

Cited by 14 publications

(7 citation statements)

References 11 publications

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“…An analysis of published reactions reveals that different electrophile pairs require different ligands for optimal reactivity and selectivity, but certain trends have emerged. For example, the c PrIndaBOX ligand ( L3 ) initially disclosed for the reductive alkenylation of benzylic chlorides has proven optimal for a variety of additional Ni-catalyzed enantioselective alkenylation reactions. − Alternatively, BiOX ligands with branched alkyl substituents (e.g., L5 ) have proven versatile for a variety of enantioselective reductive arylation reactions. ,, The origin of this divergence in the ligand framework is likely not just related to enantioinduction but also reflects the different relative rates of oxidative addition of the respective electrophiles.…”

Section: Observations and Mechanistic Insightsmentioning

confidence: 99%

Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Chen,

Reisman

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: After decades of palladium dominating the realm of transition-metal-catalyzed cross-coupling, recent years have witnessed exciting advances in the development of new nickel-catalyzed cross-coupling reactions to form C(sp 3 ) centers. Nickel possesses distinct properties compared with palladium, such as facile single-electron transfer to C(sp 3 ) electrophiles and rapid C−C reductive elimination from Ni III . These properties, among others, make nickel particularly well-suited for reductive cross-coupling (RCC) in which two electrophiles are coupled and an exogenous reductant is used to turn over the metal catalyst. Ni-catalyzed RCCs use readily available and stable electrophiles as starting materials and exhibit good functional group tolerance, which makes them appealing for applications in the synthesis of complex molecules. Building upon the foundational work in Ni-catalyzed RCCs by the groups of Kumada, Durandetti, Weix, and others, as well as the advancements in Ni-catalyzed enantioselective redox-neutral cross-couplings led by Fu and co-workers, we initiated a program to explore the feasibility of developing highly enantioselective Ni-catalyzed RCCs. Our research has also been driven by a keen interest in unraveling the factors contributing to enantioinduction and electrophile activation as we seek new avenues for advancing our understanding and further developing these reactions.In the first part of this Account, we organize our reported methods on the basis of the identity of the C(sp 3 ) electrophiles, including benzylic chlorides, N-hydroxyphthalimide (NHP) esters, and α-chloro esters and nitriles. We highlight how the selection of specific chiral ligands plays a pivotal role in achieving high cross-selectivity and enantioselectivity. In addition, we show that reduction can be accomplished not only with heterogeneous reductants, such as Mn 0 , but also with the soluble organic reductant tetrakis(dimethylamino)ethylene (TDAE), as well as electrochemically. The use of homogeneous reductants, such as TDAE, is well suited for studying the mechanism of the transformation. Although this Account primarily focuses on RCCs, we also highlight our work using trifluoroborate (BF 3 K) salts as radical precursors for enantioselective dual-Ni/photoredox systems. At the end of this Account, we summarize the relevant mechanistic studies of two closely related asymmetric reductive alkenylation reactions developed in our laboratory and provide a context between our work and related mechanistic studies by others. We discuss how the ligand properties influence the rates and mechanisms of electrophile activation and how understanding the mode of C(sp 3 ) radical generation can be used to optimize the yield of an RCC. Our research endeavors to offer insights on the intricate mechanisms at play in asymmetric Ni-catalyzed RCCs with the goal of using the rate of electrophile activation to improve the substrate scope of enantioselective RCCs. We anticipate that the insights we shar...

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Section: Observations and Mechanistic Insightsmentioning

confidence: 99%

Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Chen,

Reisman

2024

Acc. Chem. Res.

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“…In 2020, Anthony and Diao [28] reported the first asymmetric intermolecular reductive 1,2-DIAR using Apolinar and co-workers [29] developed the sulfonamide-directed Ni(COD) 2 -catalyzed 1,2-DIAR of alkenyl amines using aryl boronic esters and aryl iodides in the presence of DMFU to facilitate reductive elimination (Scheme 13). The highest product yields were provided by EWGs at the para-position of the aryl iodides, and the product yield diminished with electron-donating and -neutral groups.…”

Section: Nickel Catalysismentioning

confidence: 99%

“…In 2020, Anthony and Diao [28] reported the first asymmetric intermolecular reductive 1,2‐DIAR using activated styrenes (Scheme 12). The optimum reaction conditions employ NiBr 2 (dme) as the catalyst, i ‐Pr‐BiOx as the chiral ligand, 9‐Azabicyclo[3.3.1]nonane N ‐oxyl (ABNO) radical as an additive, and Zn as the reductant in dimethylpropyleneurea (DMPU) solvent at 50 °C for 16 hours.…”

Section: Nickel Catalysismentioning

confidence: 99%

Recent Advances in the 1,2‐Diarylation of Alkenes

Jose,

Mathew

2023

Adv Synth Catal

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Alkenes are a fascinating functional class that can be converted into various structures. A desirable and durable synthetic method for forming two C−C bonds across an olefin is the dicarbofunctionalization of olefins, catalyzed by transition metals. This method enables a rapid expansion of molecular complexity in a single step. Among the myriad of efficient strategies for alkene difunctionalization, the 1,2‐diarylation mode stands out primarily due to its remarkable ability to incorporate two hindered aryl groups across the C=C bond in a versatile and straightforward manner. This review covers the recent advances in the 1,2‐diarylation of alkenes from 2018 to 2023, focusing on different transition metals employed as catalysts.

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“…52 In recent years, the reductive strategy of dicarbofunctionalization of carbon−carbon π-frameworks with two carbon electrophiles has become an attractive alternative for simultaneously forming two vicinal C−C bonds. 12,53,54 The corresponding halides are ideal coupling partners because they are abundant, bench-stable, and readily available and eschew the need for preformed, sensitive organometallic reagents, thus improving the step and atom economy and functional group compatibility. However, asymmetric three-component arylalkylation of alkenes with two different hybridized natures of aryl and alkyl halides represents a formidable challenge due to the elusive regio-, chemo-, and stereoselectivity.…”

Section: ■ Introductionmentioning

confidence: 99%

Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence

Dong,

Xu,

Chang

et al. 2024

ACS Catal.

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Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric arylalkylation via the migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile arylalkylation of alkenes with aryl-and alkyl halides via an integrated Heck carbometalation/ radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal and internal alkenes to successfully engage the arylalkylation with exquisite control of regio-, chemo-, and stereoselectivity. More importantly, this reductive arylalkylation undergoes regio-and enantioselective arylnickelation followed by radical cross-coupling via Csp 3 −Csp 3 reductive elimination, thus exhibiting reverse regioselectivity to the radical relay method. Mild reaction conditions and exceptional functional group tolerance facilitate this method's compatibility with bioactive motifs and the modular synthesis of biologically active compounds. The control experiments and density functional theory calculations provide insights into the mechanism and origin of regio-and stereoselectivity, and the hemilabile nature of the PHOX ligand is critical for achieving this enantioselective arylalkylation.

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Asymmetric Reductive Dicarbofunctionalization of Alkenes via Nickel Catalysis

Cited by 14 publications

References 11 publications

Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Recent Advances in the 1,2‐Diarylation of Alkenes

Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence

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Asymmetric Reductive Dicarbofunctionalization of Alkenes via Nickel Catalysis

Cited by 14 publications

References 11 publications

Enantioselective C(sp2)–C(sp3) Bond Construction by Ni Catalysis

Enantioselective C(sp2)–C(sp3) Bond Construction by Ni Catalysis

Recent Advances in the 1,2‐Diarylation of Alkenes

Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence

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Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis

Enantioselective C(sp²)–C(sp³) Bond Construction by Ni Catalysis