86217-38-1Relevant articles and documents
Tuning Triplet Energy Transfer of Hydroxamates as the Nitrene Precursor for Intramolecular C(sp3)-H Amidation
Chang, Sukbok,Jung, Hoimin,Keum, Hyeyun,Kweon, Jeonguk
, p. 5811 - 5818 (2020/04/10)
Reported herein is the design of a photosensitization strategy to generate triplet nitrenes and its applicability for the intramolecular C-H amidation reactions. Substrate optimization by tuning physical organic parameters according to the proposed energy transfer pathway led us to identify hydroxamates as a convenient nitrene precursor. While more classical nitrene sources, representatively organic azides, were ineffective under the current photosensitization conditions, hydroxamates, which are readily available from alcohols or carboxylic acids, are highly efficient in accessing synthetically valuable 2-oxazolidinones and γ-lactams by visible light. Mechanism studies supported our working hypothesis that the energy transfer path is mainly operative.
One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: Theoretical evidence for an asynchronous concerted pathway
Demir, Esra,Sari, Ozlem,?etinkaya, Yasin,Atmaca, Ufuk,Erdem, Safiye Sa?,?elik, Murat
, p. 1805 - 1819 (2020/11/07)
The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained in ratios close to 1:1 in the cyclization reactions. The best yields of these compounds were obtained in dichloromethane (DCM). Together with 16 known compounds, two novel oxazolidinone derivatives and two novel cyclic carbonates were synthesized with an efficient and straightforward method. Compared to the existing methods, the synthetic approach presented here provides the following distinct advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated. The further investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates disclosed that the cycloaddition reaction proceeds via an asynchronous concerted mechanism in gas phase and in DCM.
Regioselective Ring-Opening of Styrene Oxide Derivatives Using Halohydrin Dehalogenase for Synthesis of 4-Aryloxazolidinones
Wan, Nanwei,Tian, Jiawei,Zhou, Xiaoying,Wang, Huihui,Cui, Baodong,Han, Wenyong,Chen, Yongzheng
supporting information, p. 4651 - 4655 (2019/08/27)
A biocatalytic approach towards a range of 4-aryloxazolidinones is developed using a halohydrin dehalogenase from Ilumatobacter coccineus (HheG) as biocatalyst. The method is based on the HheG-catalyzed α-position regioselective ring-opening of styrene oxide derivatives with cyanate as a nucleophile, producing the corresponding 4-aryloxazolidinones in moderate to good yields. Synthesis of enantiopure 4-aryloxazolidinones is also achievable using chiral epoxide materials. (Figure presented.).
