Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Lu, Fu‐Dong; Lu, Liang‐Qiu; He, Gui-Feng; Bai, Jun-Chuan; Xiao, Wen‐Jing

doi:10.1021/jacs.1c01260

Cited by 113 publications

(54 citation statements)

References 63 publications

(72 reference statements)

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“…The oxocyanation product 1 c was obtained together with the desired aminocyanation product 1 d , suggesting that both the aroyloxy radical and the phthalimidyl radical may be present under the reaction conditions. This result conflicts with the report that under visible‐light photocatalysis, 1 a generates a phthalimidyl radical exclusively [17e] . Interestingly, upon increasing the loading of copper from 1 mol % to 7 mol % and maintaining the loading of L at 1 mol %, the ratio of 1 c / 1 d was increased to 5.4/1 (entries 2–4).…”

Section: Resultscontrasting

confidence: 79%

Metal‐to‐Ligand Ratio‐Dependent Chemodivergent Asymmetric Synthesis

et al. 2021

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Chemodivergent asymmetric synthesis was achieved by tuning the metal‐to‐ligand ratio in an organometallic catalytic system. Using N‐(aroyloxy)phthalimide as the precursor of either an oxygen‐centered aroyloxy radical or a nitrogen‐centered phthalimidyl radical, enantioselective oxocyanation or aminocyanation of alkenes was achieved separately through a dual photoredox and copper catalysis. The metal‐to‐ligand ratio can exert chemoselective control while retaining the high enantiopurity of divergent products. Both reactions proceed efficiently with catalyst loading as low as 0.2 mol % and can be performed on a gram scale without loss of chemoselectivity or enantioselectivity. Chemodivergent asymmetric 1,5‐aminocyanation or 1,5‐oxocyanation of vinylcyclopropane can also be realized by this protocol. Mechanistic investigations involving electron paramagnetic resonance (EPR) experiments were performed to shed light on the stereochemical and chemodivergent results.

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Section: Resultscontrasting

confidence: 79%

Metal‐to‐Ligand Ratio‐Dependent Chemodivergent Asymmetric Synthesis

et al. 2021

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“…The reaction products contain one additional double bond which can be subsequently used to produce versatile functionalities. Notably, during the reviewing process of this paper, the Chen and Xiao group reported elegant photoinduced copper-catalyzed asymmetric carboesterifications of dienes with redox-active oxime esters [47][48][49] .…”

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confidence: 99%

Asymmetric radical carboesterification of dienes

et al. 2021

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The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.

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“…Then, Han et al [124] applied a similar Ir/Cu dual catalytic method, using NHP esters 1 as the alkylating agents and trimethylsilyl cyanide (TMSCN) as the cyanating agent to realize the asymmetric cyanoalkylation of alkenes under the irradiation of blue LED, which enriched the research content of asymmetric reactions involving NHP esters (Scheme 18b). Very recently, Xiao et al [125] used 1,3-dienes as the feedstocks to carry out a three-component photocatalytic reaction with NHP esters 1 and TMSCN to realize the enantioselective carbocyanation of 1,3-dienes in the similar dual catalytic system involving allylcopper intermediate (Scheme 18c). Interestingly, perylene (PC1) was employed as an organic photocatalyst in the reaction.…”

Section: Reactions Involving Iridium Photocatalystsmentioning

confidence: 99%

Advances of N-Hydroxyphthalimide Esters in Photocatalytic Alkylation Reactions

He¹,

Li²,

Chen³

et al. 2021

Chinese Journal of Organic Chemistry

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N-Hydroxyphthalimide (NHP) esters are easily available, stable, inexpensive, and highly photoactive compounds, which are derived from the corresponding carboxylic acids. In recent years, the application of NHP esters in photocatalytic decarboxylative reactions has captured huge attention. Herein, the vigorous development of photocatalytic alkylation reactions using alkyl NHP esters as alkylating reagents is summarized based on the classification of photocatalysts.

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Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Cited by 113 publications

References 63 publications

Metal‐to‐Ligand Ratio‐Dependent Chemodivergent Asymmetric Synthesis

Metal‐to‐Ligand Ratio‐Dependent Chemodivergent Asymmetric Synthesis

Asymmetric radical carboesterification of dienes

Advances of N-Hydroxyphthalimide Esters in Photocatalytic Alkylation Reactions

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