Charge‐Transfer Complex Promoted Regiospecific C−N Bond Cleavage of Vicinal Tertiary Diamines

Fu, Ying; Xu, Qian; Shi, Chun‐Zhao; Du, Zhengyin; Xiao, Caiqin

doi:10.1002/adsc.201800591

Cited by 16 publications

(6 citation statements)

References 52 publications

(13 reference statements)

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“…The activation and transformation of CÀ N bond in aliphatic cyclic amines has become a useful pathway for the construction of new CÀ N/CÀ X bonds. [136] Recently, Fu et al reported a visible light-induced ring opening of N-alkyl-4-piperidinols for the synthesis of (E)-homoallylamines with high region-and stereoselectivities (Scheme 42). [137] The transformation was promoted by charge-transfer complex (CT complex) using metal-free alizarin yellow R (AYR) as the organocatalyst under mile conditions.…”

Section: Photoinduced Radical-radical Cross-coupling Reactions Promotmentioning

confidence: 99%

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Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

et al. 2021

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Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages of operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with the extensive applications in the fields of organic, pharmaceutical and functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for the generation of their excited states to perform the successive oxidative or reductive reactions through the single electron transfer (SET) or energy transfer (ET) process. Furthermore, the exploration of a colored electron donor-acceptor (EDA) complex or a charge transfer (CT) complex between an electron-rich and an electron-poor substrate provides the chance to deliver the excited intermediate under the irradiation of light, resulting in the formation of radical activate species through a single electron transfer to induce successive various radical reactions. These reactions were performed without the need of any external photocatalysts under mild reaction conditions. Herein, this review focuses on the recent progress on photoinduced radical addition reactions, radical borylations, reductive reactions, radical-radical cross-coupling reactions, degradation reactions and radical cascade cyclization via EDA complexes. We highlight these novel green synthetic methodologies and applications, as well as the mechanisms. This review will help to provide references for organic and medicinal chemists who are charmed by these green organic photochemical transformations based on EDA complexes.

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Section: Photoinduced Radical-radical Cross-coupling Reactions Promotmentioning

confidence: 99%

“…The activation and transformation of C−N bond in aliphatic cyclic amines has become a useful pathway for the construction of new C−N/C−X bonds [136] . Recently, Fu et al.…”

Section: Photoinduced Radical‐radical Cross‐coupling Reactions Promot...mentioning

confidence: 99%

Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

et al. 2021

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“…Indeed, the diamines worked as N-donor ligands and chiral auxiliaries with many of metal ions such as Ca [7], Fe [8], Ag [9], Ni [10], Pd [11], and Rh [12], indeed, it explored in various catalyzed protocols and were successively employed as efficient catalysts for many transformations in organic synthesis. In this aspect, the aminals (gem-diamines) have been considered as promising electrophiles in metal-catalyzed nucleophilic addition reactions [13].…”

Section: Introductionmentioning

confidence: 99%

X-ray Crystal Structure and Hirshfeld Analysis of Gem-Aminals-Based Morpholine, Pyrrolidine, and Piperidine Moieties

et al. 2020

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The gem-aminals of 1,2-dimorpholinoethane (1) and 1-morpholino-3-morpholinium bromide propane (2) were synthesized by reaction of two molar ratio of morpholine with the halogenating agents in the presence of basic condition (K2CO3) in acetone at room temperature (RT) overnight. The structures of the centro-symmetric compound 1 and the morpholinium salt derivative 2 were assigned unambiguous by single crystal X-ray diffraction analysis and compared with the 1,2-di(pyrrolidin-1-yl)ethane 3 and 1,2-di(piperidin-1-yl)ethane 4. The 1,2-dimorpholinoethane molecule has a center of symmetry at the midpoint of the C-C bond of the ethyl moiety leading to two equivalent halves. It crystallized in monoclinic crystal system and P21/n space group, while the unit cell parameters are determined to be a = 6.0430(3), b = 8.0805(3), c = 11.1700(4) Å, and β = 97.475(2)° with unit cell volume of 540.80(4) Å3 and Z = 2 at 170(2) K. The less symmetric analogue 2 crystallized in the lower space group P21 with unit cell parameters of a = 6.37450(10), b = 11.1378(2), c = 9.6549(2) Å, and β = 93.358(2)°, while the unit cell volume is 684.30(2)Å3 at 120(2) K. Using Hirshfeld analysis, the molecules of 1 are mainly packed by weak N…H (4.2%), O…H (16.8%), and H…H (79.0%) interactions. In contrast, the molecules of 2 are packed by significantly short O…H (14.4%) and Br…H (11.6%) interactions in addition to the relatively long H…H (73.3%) interactions. DFT calculations predicted the molecular geometry of the studied compounds showing a good agreement with the experimental X-ray structures. Due to symmetry considerations, compounds 1, 3, and 4 are nonpolar with zero dipole moment, while the less symmetric molecule 2 has a dipole moment of 6.914 Debye. Their electronic aspects, such as natural population charges, HOMO, and LUMO energies as well as the corresponding reactivity descriptors, were also calculated and discussed.

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“…[3] The CÀ N bond cleavage reaction of 1,2,3,4-tetrahydroisoquinolines and N,N'diarylimidazolines with tert-butylnitrite under O 2 atmosphere was developed to generate the corresponding N-nitrosoaminocarbonyl compounds (Scheme 1C). [4] Recently, a photoredox-catalyzed CÀ N bond cleavage of cyclic amines bearing a urea group, which features the hydrogen bonding interaction with nucleophiles (Scheme 1D(a)) [5] and charge-transfer promoted CÀ N bond cleavage of trialkyl amines with sulfonyl chlorides (Scheme 1D(b)) [6] have been reported. On the other hand, we were able to achieve several oxidative transformations via umpolung of bromide reactivity, including bromocyclization, [7] direct CÀ H oxidation, [8] and dual functionalization.…”

mentioning

confidence: 99%

Formal Ring Contraction of Cyclic N‐Sulfonamides via C−N Bond Cleavage and α‐Amination by Oxidation of Halides

2020

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An oxidative CÀ N bond cleavage reaction of substituted cyclic sulfonamides that proceeds via oxidation of bromide ion in hydrogen bromide solution was developed to furnish N-sulfonamideprotected acyclic amino ketones in high yields. The subsequent α-amination of the amino ketones via the oxidation of iodide in tetrabutylammonium iodide provided 2-acyl cyclic sulfonamides in good yields. The combination of these transformations involving the oxidation of halides resulted in a formal ring contraction of substituted cyclic amides.

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Charge‐Transfer Complex Promoted Regiospecific C−N Bond Cleavage of Vicinal Tertiary Diamines

Cited by 16 publications

References 52 publications

Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

X-ray Crystal Structure and Hirshfeld Analysis of Gem-Aminals-Based Morpholine, Pyrrolidine, and Piperidine Moieties

Formal Ring Contraction of Cyclic N‐Sulfonamides via C−N Bond Cleavage and α‐Amination by Oxidation of Halides

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