2017
DOI: 10.1021/acs.orglett.7b00826
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Iminoxyl Radical-Promoted Oxycyanation and Aminocyanation of Unactivated Alkenes: Synthesis of Cyano-Featured Isoxazolines and Cyclic Nitrones

Abstract: A novel and facile approach to vicinal oxycyanation and aminocyanation of internal unactivated alkenes is developed. This method utilizes the dichotomous reactivity of iminoxyl radical derived from the initiation of β,γ- and γ,δ-unsaturated ketoximes to provide the general difunctionalization of internal alkenes using tert-butyl hydroperoxide (TBHP) as the environmentally friendly oxidant, CuCN as the commercially available cyanating reagent, and pentamethyldiethylenetriamine (PMDETA) as the ligand. By using t… Show more

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Cited by 73 publications
(23 citation statements)
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“…To date, numerous methods for the synthesis of aromatic nitriles have been developed, and they can be divided into three categories according to cyanating reagent: nucleophilic‐, electrophilic‐ and radical‐cyanation . The cyanides used in nucleophilic cyanation include KCN, CuCN, NaCN, K 4 [Fe(CN) 6 ], etc (Scheme a), which have the risk of generating hazardous HCN and leading to environmental pollution. On the other hand, the cyanating reagents employed in electrophilic cyanation (Scheme b), such as 1‐cyanobenzotriazole (BtCN)– and PhOCN, are usually prepared from ClCN or BrCN that possess safety issue.…”
Section: Methodsmentioning
confidence: 99%
“…To date, numerous methods for the synthesis of aromatic nitriles have been developed, and they can be divided into three categories according to cyanating reagent: nucleophilic‐, electrophilic‐ and radical‐cyanation . The cyanides used in nucleophilic cyanation include KCN, CuCN, NaCN, K 4 [Fe(CN) 6 ], etc (Scheme a), which have the risk of generating hazardous HCN and leading to environmental pollution. On the other hand, the cyanating reagents employed in electrophilic cyanation (Scheme b), such as 1‐cyanobenzotriazole (BtCN)– and PhOCN, are usually prepared from ClCN or BrCN that possess safety issue.…”
Section: Methodsmentioning
confidence: 99%
“…In 2018, Han's group reported oxycyanation of β,γ‐unsaturated oximes for the construction of cyano‐substituted isoxazolines by using tert ‐butyl hydroperoxide (TBHP) as oxidant, CuCN as the easily available cyano source, and pentamethyldiethylenetriamine (PMDETA) as the ligand (Scheme 24). [36] Other cuprous salts such as CuCl, CuBr, and CuI were suitable for this transformation, then the corresponding oxyhalogenation products were acquired in good yields. Additionally, when β,γ‐unsaturated oximes reacted with KSCN using Cu(OAc) 2 as the catalyst, the resulting thiocyano‐substituted isoxazolines were also obtained.…”
Section: Radical Strategies For Cyclization Of βγ‐Unsaturated Hydrazones and Oximesmentioning
confidence: 99%
“…Oxidative cyclization of unsaturated oximes with the formation of isoxazolines or cyclic nitrones and the introduction of a nitrile group was achieved using the CuCN/N,N,N′,N′′,N′′pentamethyldiethyltriamine (PMDETA)/TBHP system (Scheme 50) [139]. Other aliphatic amine ligands (N,N,N′,N′tetramethylethylenediamine and 1,1,4,7,10,10-hexamethyltriethylenetetramine) showed moderate results and aromatic nitrogen-containing ligands (2,2'-bipyridine and phenanthroline) were even less efficient for the synthesis of target the isoxazolines.…”
Section: Both Aliphatic (Example 118c) and Aromatic (Examplesmentioning
confidence: 99%