title: Redox-Neutral α-Arylation of Alkyl Nitriles with Aryl Sulfoxides: A Rapid Electrophilic Rearrangement.
abstract: A facile α-arylation of nitriles has been developed by simply introducing Tf2O and DABCO to the mixture of nitriles and aryl sulfoxides. The transformation consists of two sequential steps: (i) Tf2O-initiated electrophilic assembly and and (ii) DABCO-triggered rearrangement. Each step can be tuned independently by changing the temperature and/or base. This adjustability allows the method to accommodate a wide range of substrates. Notable features of this new protocol include remarkable efficiency (20 min, -30 °C), exclusive regioselectivity, and high functional group compatibility, which can be challenging issues in traditional approaches. NMR studies not only identified a unique, highly unstable sulfonium imine complex but also demonstrated the importance of temperature in the formation and manipulation of this key intermediate. Further DFT calculations suggested that an electrophilic assembly, followed by removal of HOTf (by base), and finally [3,3]-sigmatropic rearrangement are three key stages in the reaction. The versatile transformability of the products and easy scalability of this reaction are also exhibited here.
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Li
authors.initials: L
authors.lastname: Shang
authors.affiliation: College of Chemistry and Chemical Engineering, Hainan Normal University , 99 Longkunnan Road, Haikou, 571158, China.
authors.forename: Yonghui
authors.initials: Y
authors.lastname: Chang
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Fan
authors.initials: F
authors.lastname: Luo
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Jia-Ni
authors.initials: JN
authors.lastname: He
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Xin
authors.initials: X
authors.lastname: Huang
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Lichun
authors.initials: L
authors.lastname: Kong
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
authors.forename: Kaixiao
authors.initials: K
authors.lastname: Li
authors.affiliation: Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.|State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian 116024, China.
authors.forename: Bo
authors.identifier: 0000-0002-8237-6698
authors.initials: B
authors.lastname: Peng