Access to 1,3‐Dinitriles by Enantioselective Auto‐tandem Catalysis: Merging Allylic Cyanation with Asymmetric Hydrocyanation

Long, Jinguo; Yu, Ruobing; Gao, Jihui; Fang, Xianjie

doi:10.1002/ange.202000704

Cited by 10 publications

(2 citation statements)

References 90 publications

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“…To showcase the potential synthetic utility of this asymmetric method in the construction of valuable skeletons, we performed diverse further transformations with the chiral β-cyano ketones and alkyldinitriles (Fig. 5) [65][66] . For example, the cyano group of 6ba and 7ia could be easily converted to amide group by Pd-catalyzed hydrolysis using stoichiometric acetaldoxime in re uxing aqueous EtOH, giving the corresponding products 8 and 9 with good yields, respectively (Fig.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

Xiao

Wang

Gao

et al. 2020

Preprint

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An intermolecular, enantioselective three-component radical vicinal dicarbofunctionalization reaction of olefins enabled by merger of radical addition and cross-coupling using photoredox and copper dual catalysis is presented here. Key to the success of this protocol relies on chemoselective addition of acyl and cyanoalkyl radicals, generated in situ from the redox-active oxime esters by a photo-catalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto the alkenes to form new carbon radicals. Single electron metalation of such newly formed carbon radicals to TMSCN-derived L1Cu(II)(CN)2 complex leads to asymmetric cross-coupling. This three-component process proceeds under mild conditions, and tolerates a diverse range of functionalities and synthetic handles, leading to valuable optically active β–cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (> 60 examples, up to 97% ee).

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Section: Resultsmentioning

confidence: 99%

Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

Xiao

Wang

Gao

et al. 2020

Preprint

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“…[14] Among numerous approaches, catalytic hydrocyanation reaction is arguably the most efficient and atomeconomic protocol to synthesize nitriles. [15] Driven by our continuous interest in the hydrocyanation reaction, [16] we started to investigate the hydrocyanation of nonconjugated dienes via the chain-walking strategy. However, two challenging issues need to be addressed: 1) the preferential migration of one C = C double bond over the other in one molecule should be controlled; 2) the regio-, chemo-and stereoselec-tivity outcome of the functionalization of the conjugated diene intermediate after the chain-walking process should also be controlled (Scheme 1 c).…”

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confidence: 99%

Enantioselective Nickel‐Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes

Rajasekar

Fang

2020

Angew Chem Int Ed

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Metal-catalyzed chain-walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chainwalking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel-catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain-walking process is demonstrated. The reaction exhibits excellent regio-and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium-labeling experiments support the chain-walking process, which involves an iterative b-H elimination and reinsertion processes. Gram-scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation. Scheme 1. State of the art and scope of the current work.

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Auto Tandem Catalysis: Asymmetric Vinylogous Cycloaddition/Kinetic Resolution Sequence for the Enantioselective Synthesis of Spiro‐Dihydropyranone from Benzylidene Meldrum's Acid

et al. 2021

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A catalytic enantioselective vinylogous domino reaction has been achieved from ketone-derived benzylidene Meldrum's acid and α-ketolactones to provide spirolactone dihydropyranones with more than 99% ee. An Auto Tandem Catalysis (ATC) process resulting from dual and complementary role of (DHQ)2PHAL organocatalyst resulted in a sequence involving an asymmetric vinylogous formal (4+2) cycloaddition of benzylidene and the subsequent kinetic resolution operating through a 1,3prototropic shift leading to good yields (> 50%) and the high selectivity.

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Access to 1,3‐Dinitriles by Enantioselective Auto‐tandem Catalysis: Merging Allylic Cyanation with Asymmetric Hydrocyanation

Cited by 10 publications

References 90 publications

Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

Enantioselective Nickel‐Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes

Auto Tandem Catalysis: Asymmetric Vinylogous Cycloaddition/Kinetic Resolution Sequence for the Enantioselective Synthesis of Spiro‐Dihydropyranone from Benzylidene Meldrum's Acid

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