Selective C-N σ Bond Cleavage in Azetidinyl Amides under Transition Metal-Free Conditions

Li, Hengzhao; Lai, Zemin; Adijiang, Adila; Zhao, Hongye; An, Jie

doi:10.3390/molecules24030459

Cited by 11 publications

(4 citation statements)

References 34 publications

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“…Increasing the amount of Na to 7 equiv did not improve the yield (Table , entry 3). The Na/15-crown-5/EtOH system was then tested . However, the addition of crown ether was not beneficial in the reaction, and no product was obtained under the Na/15-crown-5-mediated outer-sphere electron-transfer conditions (Table , entries 2 and 4).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source

Lei

Lai

et al. 2021

J. Org. Chem.

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Selective introduction of the deuterium atom into the α-position of amines is important for the development of all types of novel deuterated drugs and agrochemicals due to the pervasive presence of amines. In this study, we report the first general single-electron-transfer reductive deuteration of both ketoximes and aldoximes using SmI2 as an electron donor and D2O as a deuterium source for the synthesis of α-deuterated primary amines with excellent levels of deuterium incorporations (>95% [D]). This protocol exhibits excellent chemoselectivity and tolerates a variety of functional groups. The potential application of this new method was showcased in the synthesis of deuterated drugs, such as rimantadine-d 4, the tebufenpyrad analogue, derivatives of nabumetone and pregnenolone, and a series of building blocks for the rapid and general assembly of deuterated drugs and pesticides.

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Section: Resultsmentioning

confidence: 99%

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source

Lei

Lai

et al. 2021

J. Org. Chem.

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“…The An group also investigated the chemoselective C-N bond cleavage of the four-membered ring in azetidinyl amides using sodium dispersion (particle size 5-10 m) and 15-crown-5 at 0 °C (Scheme 18). 44 Potentially competing Birch reduction of the aromatic ring could be prevented in the absence of a proton donor. The reaction proceeds selectively at the azetidinyl site because of the large ring strain (25.4 kcal/mol), while other five-and six-membered cyclic amides and acyclic tertiary and secondary amides did not react under these conditions.…”

Section: Scheme 17 C-n and C-o Bond Cleavage Of Carboxamides With Sdmentioning

confidence: 99%

Recent Advances in the Use of Sodium Dispersion for Organic Synthesis

De¹,

Asako²,

Ilies³

2021

Synthesis

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This short review describes the recent emergence of organosodium chemistry, motivated by the requirements of modern synthetic chemistry for sustainability, and powered by the use of sodium dispersion, a form of sodium that is commercially available, easy to handle, and has a large active surface area. We present recent preparation methods of oraganosodium compounds using sodium dispersion, and their applications to synthesis; sodium amides and phosphides are also briefly discussed.

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“…Recently, our group has developed a practical and ammonia-free method for the preparation of sodium electride using sodium dispersions and 15-crown-5 . Sodium dispersion (5–10 μm) in mineral oil is a bench-stable and commercially available reagent .…”

Section: Introductionmentioning

confidence: 99%

Reductive Cleavage of Unactivated Carbon–Cyano Bonds under Ammonia-Free Birch Conditions

Ding

Luo

et al. 2019

J. Org. Chem.

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A general protocol for the reductive cleavage of unactivated carbon–cyano bonds in aliphatic nitriles has been achieved under single-electron-transfer conditions using Na/15-crown-5/H2O. Electron is supplied by the electride derived from bench-stable sodium dispersions and recoverable 15-crown-5. H2O provides the proton source and suppresses the reduction of aromatic moieties. Compared with the Na/NH3 electride system generated under traditional Birch conditions, this ammonia-free electride system is more practical and features better reactivity and chemoselectivity for the decyanations of a broad range of aliphatic nitriles.

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Selective C-N σ Bond Cleavage in Azetidinyl Amides under Transition Metal-Free Conditions

Cited by 11 publications

References 34 publications

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source

Recent Advances in the Use of Sodium Dispersion for Organic Synthesis

Reductive Cleavage of Unactivated Carbon–Cyano Bonds under Ammonia-Free Birch Conditions

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Selective C-N σ Bond Cleavage in Azetidinyl Amides under Transition Metal-Free Conditions

Cited by 11 publications

References 34 publications

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D2O as a Deuterium Source

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D2O as a Deuterium Source

Recent Advances in the Use of Sodium Dispersion for Organic Synthesis

Reductive Cleavage of Unactivated Carbon–Cyano Bonds under Ammonia-Free Birch Conditions

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Product

Resources

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Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source

Synthesis of α-Deuterated Primary Amines via Reductive Deuteration of Oximes Using D₂O as a Deuterium Source