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

Ding, Yuxuan; Luo, Shihui; Ma, Lifu; An, Jie

doi:10.1021/acs.joc.9b02028

Cited by 17 publications

(5 citation statements)

References 58 publications

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“…The reason for this orientation is that the cyano group, which is a highly polarized substituent and responsible for the dipolar character of 5CB, exposes the partially positive cyano-carbon to the dangling bonds of the monovacancy carbon atoms, maximizing the likelihood to induce a reactive event. This commonly occurs in reductive elimination reactions of cyano functional groups [ 53 , 54 ]. As is shown in Figure 1 a, however, the computed binding energy increases monotonically as 5CB approaches, suggesting that there is no chemical bonding between the 5CB and the monovacancy in the planar orientation.…”

Section: Resultsmentioning

confidence: 99%

Insertion of the Liquid Crystal 5CB into Monovacancy Graphene

et al. 2022

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Interfacial interactions between liquid crystal (LC) and two-dimensional (2D) materials provide a platform to facilitate novel optical and electronic material properties. These interactions are uniquely sensitive to the local energy landscape of the atomically thick 2D surface, which can be strongly influenced by defects that are introduced, either by design or as a byproduct of fabrication processes. Herein, we present density functional theory (DFT) calculations of the LC mesogen 4-cyan-4′-pentylbiphenyl (5CB) on graphene in the presence of a monovacancy (MV-G). We find that the monovacancy strengthens the binding of 5CB in the planar alignment and that the structure is lower in energy than the corresponding homeotropic structure. However, if the molecule is able to approach the monovacancy homeotropically, 5CB undergoes a chemical reaction, releasing 4.5 eV in the process. This reaction follows a step-by-step process gradually adding bonds, inserting the 5CB cyano group into MV-G. We conclude that this irreversible insertion reaction is likely spontaneous, potentially providing a new avenue for controlling both LC behavior and graphene properties.

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Section: Resultsmentioning

confidence: 99%

Insertion of the Liquid Crystal 5CB into Monovacancy Graphene

et al. 2022

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“…This limitation was addressed by An and co‐workers, who reported a protocol for the reductive cleavage of unactivated C−CN bonds in aliphatic nitriles using Na/15‐crown‐5 and H 2 O (Scheme 12). [28] Electron is supplied by the electride derived from bench‐stable sodium dispersions and recoverable 15‐crown‐5. H 2 O, which is the proton source in this reaction, also suppresses the reduction of aromatic moieties.…”

Section: Hydrodecyanationmentioning

confidence: 99%

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Paul

Patra

2021

Asian J Org Chem

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Nitrile is one of the ubiquitous functional groups in natural products and polymer industry. It is often used as a versatile building block in synthetic chemistry. Classically, nitrile group is used for alpha functionalization, orthoÀ CÀ H activation and as a precursor for amine or carbonyl functionalities. With the development of various transition metal catalyzed methods, in the last two decades, nitrile group has emerged as a source of carbon synthons through CÀ CN bond activation despite of its high bond energy. In this review we have summarized all recent developments involving the carbon synthons arising from the cleavage of CÀ CN bonds. Depending on the fate of the carbon center after cleavage, all the reactions are classified in two major categories for the ease of discussion: 1) decyanation (removal of the nitrile group) and 2) decyanative functionalization (replacement of the nitrile group). Finally, current limitations in CÀ CN bond activation strategies and future prospects are discussed.

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“…crown-5 (Scheme 19). 45 For nitriles possessing an aromatic group, H 2 O plays a crucial role in switching the chemoselectivity from arene reduction to decyanation. The reaction was limited to aliphatic nitriles, but heterocycles such as indole and benzimidazole were tolerated.…”

Section: Special Topic Synthesismentioning

confidence: 99%

“…The An group further applied the reaction system to an ammonia-free decyanation of aliphatic nitriles via homolytic reductive cleavage of the C-CN bond in the presence of sodium dispersion (particle size 5-10 µm) and 15-crown-5 (Scheme 19). 45 For nitriles possessing an aromatic group, H2O plays a crucial role to switch the chemoselectivity from arene reduction to decyanation. The reaction was limited to aliphatic nitriles, but heterocycles such as indole and benzimidazole were tolerated.…”

Section: Scheme 18 C-n Bond Cleavage Of Azetidinyl Amides With Sd and 15-crown-5mentioning

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

Cited by 17 publications

References 58 publications

Insertion of the Liquid Crystal 5CB into Monovacancy Graphene

Insertion of the Liquid Crystal 5CB into Monovacancy Graphene

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Recent Advances in the Use of Sodium Dispersion for Organic Synthesis

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