3662-78-0Relevant articles and documents
Integrated Synthesis Using Isothiocyanate-Substituted Aryllithiums by Flow Chemistry
Lee, Hyune-Jea,Torii, Daiki,Jeon, Yongju,Yoshida, Jun-Ichi,Kim, Heejin
supporting information, p. 1899 - 1902 (2020/09/11)
The isothiocyanate (NCS) group is an attractive functional group in the field of organic and pharmaceutical chemistry. It can be transformed into other heteroatomic functional groups. It usually acts as the inductive group of biological activity and has also been traditionally used as the fluorescent-labeling reagent. However, it is not compatible with strong bases. When the NCS group is at para position in halobenzenes, it generally undergoes nucleophilic additions upon reaction with strong bases. To the best of our knowledge, there is currently no general methodology for the formation and reactions of NCS-functionalized aryllithiums for meta and para substituents. Herein, we report the continuous-flow generation of NCS-substituted aryllithiums from the corresponding haloarenes via a selective halogen-lithium exchange reaction and its reaction with various electrophiles to yield NCS-containing products. We also achieved an integrated synthesis through sequential reactions of the NCS-containing compounds with additional nucleophiles using the continuous-flow reactors.
Investigation of (Me4N)SCF3 as a Stable, Solid and Safe Reservoir for S=CF2 as a Surrogate for Thiophosgene
Scattolin, Thomas,Pu, Maoping,Schoenebeck, Franziska
supporting information, p. 567 - 571 (2018/01/26)
While thiophosgene finds widespread usage on a multi-ton scale, its fluorinated counterpart S=CF2 is essentially unexplored in synthesis. Using experimental reactivity tests, ReactIR and computational techniques, we herein showcase that the solid (Me4N)SCF3 functions as a safe reservoir for S=CF2. A key feature is that the reactive electrophile is not simply released over time, but instead is liberated under activation with a protic nucleophile. The reactivity of S=CF2 is mild, allowing large-scale and late-stage synthetic applications without special reaction control. The mechanism was fully elucidated, including a rationalization of the role of the Me4N cation and the origins of selectivity.
Synthesis of Isothiocyanates and Unsymmetrical Thioureas with the Bench-Stable Solid Reagent (Me4N)SCF3
Scattolin, Thomas,Klein, Alexander,Schoenebeck, Franziska
supporting information, p. 1831 - 1833 (2017/04/11)
A highly efficient, selective, and rapid transformation of primary amines and diamines to isothiocyanates and cyclic thioureas is disclosed. As opposed to established approaches that employ toxic or volatile electrophilic liquids and require reaction control (i.e., slow addition, cooling), this protocol utilizes the bench-stable, solid reagent (Me4N)SCF3 at room temperature. The method is characterized by operational simplicity, high speed, efficiency, high functional group tolerance, and late-stage applicability. The byproducts are solids, allowing isolation of the target compounds by filtration.