Copper-catalyzed ring-opening C(sp<sup>3</sup>)–N coupling of cycloketone oxime esters: access to 1°, 2° and 3° alkyl amines

Tian, Li; Gao, Shuangqiu; Wang, Rui; Yang, Li; Tang, Chunlin; Shi, Lili; Fu, Junkai

doi:10.1039/c9cc02030f

Cited by 39 publications

(14 citation statements)

References 54 publications

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“…The desired cyano‐containing alkyl amines were synthesized in good to excellent yields and have proven to be versatile synthetic building blocks for multifarious organic compounds (See Figure 97). [103] …”

Section: Miscellaneous Cyanation Techniquesmentioning

confidence: 99%

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

et al. 2021

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Earth‐abundant transition metal based catalytic materials can become pivotal for clean chemical manufacturing due to their facile handling and air moisture stability replacing conventional expensive noble metal based catalytic systems. Amongst the non‐noble metals, copper based catalytic systems due to the variable oxidation states have been effectively used as the tunable and multifunctional catalytic materials for the promotion of selective organic transformations. These copper based catalytic systems effectively promote multifarious organic transformations promoting functionalization of the easily available organic substrates. Nitriles are a significant class of nitrogen‐containing compounds finding applications in pharmaceutical and fine chemical industries. Several organic and inorganic cyanide sources have been effectively usedto cyanate organic compounds by using multi‐ferrous copper catalysts. Furthermore, nitrile compounds are key components used for the synthesis of drug molecules and fabrication of functionalized materials.

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Section: Miscellaneous Cyanation Techniquesmentioning

confidence: 99%

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

et al. 2021

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“…Based on the above observations and previous reports 60–66,68,69 , the proposed mechanisms of two catalytic processes were depicted in Fig. 6.…”

Section: Resultsmentioning

confidence: 59%

Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles

Wang

et al. 2019

Nat Commun

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Ring-opening reaction via selective cleavage of C–C bond is known as a powerful strategy for construction of complex molecules. Complementary to the ionic process focusing on mostly small ring systems, radical-mediated C–C bond cleavage offers a solution for further diverse enantioselective functionalization benefited from its mild conditions, whereas such asymmetric transformations are still limited to three-membered rings so far. Herein, we describe radical-mediated ring-opening and enantioselective cyanation of four- and five-membered cycloketone oxime esters to access chiral 1,5- and 1,6-dinitriles. Employment of dual photoredox/copper catalysis is essential for the asymmetric ring-opening cyanation of cyclopentanone oxime esters. Both reactions proceed under mild conditions giving chiral dinitriles in high yields and enantioselectivity with low catalyst loading and broad substrate scope. The products dinitriles can be converted to valuable optically active diamides and diamines. Mechanistic studies indicate that the benzylic radical generated via C–C single bond cleavage is involved in the catalytic cycle.

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“…For example, Liu reported the copper-catalyzed C-N bond formation of free anilines and cyclobutanone oxime esters with 6,6′-dimethyl-2,2′-bipyridine 162 as the ligand, 61 while Fu and co-workers found that a Cu(OTf) 2 /1,10-phen catalytic system was more effective for secondary amines. 62 In a report by Shi, the use of fac-Ir(ppy) 3 under visible light irradiation can promote the reaction of secondary amines. 63 Depending on the nature of the amines, Guo systemically investigated the copper-catalyzed ring-opening amination of cycloketone oxime esters using different ligands with or without visible light irradiation.…”

Section: C-n Bond Formationmentioning

confidence: 99%

Iminyl-Radical-Triggered C–C Bond Cleavage of Cycloketone Oxime Derivatives: Generation of Distal Cyano-Substituted Alkyl Radicals and Their Functionalization

et al. 2020

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Alkyl nitriles are versatile building blocks in organic synthesis because the cyano group can be easily converted into other functional groups. Iminyl-radical-triggered C–C bond cleavage of cycloketone oxime derivatives provides a practical route to access distal cyano-substituted alkyl radicals, which has given chemists a new radical reaction platform for the synthesis of diverse alkyl nitriles. This review provides an overview of various types of radical cyanoalkylation via ring opening of cycloketone oxime derivatives.1 Introduction2 C–C Bond Formation2.1 Alkenes as Radical Acceptors2.2 Aromatic Rings as Radical Acceptors2.3 Organometallic Reagents as Radical Acceptors2.4 Cyanoalkyl-Radical-Triggered Cyclization Reactions2.5 Miscellaneous3 C–Heteroatom Bond Formation3.1 C–O Bond Formation3.2 C–N Bond Formation3.3 C–S Bond Formation3.4 C–Halogen Bond Formation3.5 C–B Bond Formation4 Conclusion

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Copper-catalyzed ring-opening C(sp³)–N coupling of cycloketone oxime esters: access to 1°, 2° and 3° alkyl amines

Abstract: Access to 1°, 2° and 3° alkyl amines through copper-catalyzed C(sp3)–N coupling of cycloketone oxime esters was realized.

Cited by 39 publications

References 54 publications

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles

Iminyl-Radical-Triggered C–C Bond Cleavage of Cycloketone Oxime Derivatives: Generation of Distal Cyano-Substituted Alkyl Radicals and Their Functionalization

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Copper-catalyzed ring-opening C(sp3)–N coupling of cycloketone oxime esters: access to 1°, 2° and 3° alkyl amines

Abstract: Access to 1°, 2° and 3° alkyl amines through copper-catalyzed C(sp3)–N coupling of cycloketone oxime esters was realized.

Cited by 39 publications

References 54 publications

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

Enantioselective cyanation via radical-mediated C–C single bond cleavage for synthesis of chiral dinitriles

Iminyl-Radical-Triggered C–C Bond Cleavage of Cycloketone Oxime Derivatives: Generation of Distal Cyano-Substituted Alkyl Radicals and Their Functionalization

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Copper-catalyzed ring-opening C(sp³)–N coupling of cycloketone oxime esters: access to 1°, 2° and 3° alkyl amines