Electron Transfer Reduction of Nitriles Using SmI2–Et3N–H2O: Synthetic Utility and Mechanism

Szostak, Michal; Sautier, Brice; Spain, Malcolm; Procter, David J.

doi:10.1021/ol403668e

Cited by 61 publications

(42 citation statements)

References 50 publications

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“…Hemiaminals 3 can be isolated when using t BuOH with SmI 2 and LiBr. After Lewis‐acid facilitated elimination of the hemiaminal, two‐electron reduction of amidiniums 6 and protonation gives the cyclic aminals 2 . Alternatively, direct reduction of 3 by SmI 2 /H 2 O to give a stable aminal radical which is further reduced to give 2 after protonation, is also possible …”

Section: Resultsmentioning

confidence: 99%

Selective Electron Transfer Reduction of Urea‐Type Carbonyls

Huang

Procter

2018

Eur J Org Chem

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Urea‐type carbonyls in barbiturates undergo a highly chemoselective electron transfer reduction upon treatment with SmI2/H2O/LiBr. The process involves the formation, and further reduction, of unusual ketyl‐type radical anions under mild conditions. Cyclic aminal products are obtained in good to excellent yield without recourse to preactivation of the substrate or the use of metal hydride reagents. Furthermore, varying the protic additive used in conjunction with SmI2 allows intermediate hemiaminals to be obtained.

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Section: Resultsmentioning

confidence: 99%

Selective Electron Transfer Reduction of Urea‐Type Carbonyls

Huang

Procter

2018

Eur J Org Chem

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“…Similarly, α-hydroxy-N-acyl-carbamides generate Nacyliminiums that may be trapped by a variety of nucleophiles, including azidotrimethylsilane, to produce the corresponding azido uracil derivative in high yields and moderate diastereoselectivity (eq 53). 140 The same reaction is possible with aza-diketopiperazines as substrates. 141 (53) Amination of Aryl Halides.…”

Section: Addition To N-acyliminium Ionsmentioning

confidence: 95%

Azidotrimethylsilane

Nishiyama

Wang

Lebel

2016

Encyclopedia of Reagents for Organic Synthesis

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“…Procter and co‐workers reported the reduction of nitriles to the corresponding primary amines under single electron transfer conditions using complex 63 (Kagan’s reagent) activated with Lewis bases 50. The catalytic system features excellent functional group tolerance and represents an attractive alternative to the use of pyrophoric alkali metal hydrides.…”

Section: Catalytic Reductions Of Nitrilesmentioning

confidence: 99%

Water Electrolysis with a Conducting Carbon Cloth: Subthreshold Hydrogen Generation and Superthreshold Carbon Quantum Dot Formation

et al. 2014

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A conducting carbon cloth, which has an interesting turbostratic microstructure and functional groups that are distinctly different from other ordered forms of carbon, such as graphite, graphene, and carbon nanotubes, was synthesized by a simple one-step pyrolysis of cellulose fabric. This turbostratic disorder and surface chemical functionalities had interesting consequences for water splitting and hydrogen generation when such a cloth was used as an electrode in the alkaline electrolysis process. Importantly, this work also gives a new twist to carbon-assisted electrolysis. During electrolysis, the active sites in the carbon cloth allow slow oxidation of its surface to transform the surface groups from COH to COOH and so forth at a voltage as low as 0.2 V in a two-electrode system, along with platinum as the cathode, instead of 1.23 V (plus overpotential), which is required for platinum, steel, or even graphite anodes. The quantity of subthreshold hydrogen evolved was 24 mL cm(-2) h(-1) at 1 V. Interestingly, at a superthreshold potential (>1.23 V+overpotential), another remarkable phenomenon was found. At such voltages, along with the high rate and quantity of hydrogen evolution, rapid exfoliation of the tiny nanoscale (5-7 nm) units of carbon quantum dots (CQDs) are found in copious amounts due to an enhanced oxidation rate. These CQDs show bright-blue fluorescence under UV light.

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Electron Transfer Reduction of Nitriles Using SmI₂–Et₃N–H₂O: Synthetic Utility and Mechanism

Cited by 61 publications

References 50 publications

Selective Electron Transfer Reduction of Urea‐Type Carbonyls

Selective Electron Transfer Reduction of Urea‐Type Carbonyls

Azidotrimethylsilane

Water Electrolysis with a Conducting Carbon Cloth: Subthreshold Hydrogen Generation and Superthreshold Carbon Quantum Dot Formation

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