- Palladium-catalyzed insertion reactions of isocyanides into thiocarbamates and selenocarbamates
-
The insertion reaction of isocyanides with thiocarbamates and selenocarbamates in the presence of a Pd(0) catalyst to selectively give 2-oxoethanimidothioates and -selenoates is reported. This is the first example of the insertion of an isocyanide into a
- Shiro, Daisuke,Fujiwara, Shin-Ichi,Tsuda, Susumu,Iwasaki, Takanori,Kuniyasu, Hitoshi,Kambe, Nobuaki
-
-
Read Online
- Electrochemically Catalyzed Newman-Kwart Rearrangement: Mechanism, Structure-Reactivity Relationship, and Parallels to Photoredox Catalysis
-
The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as "electrochemical catalysis", is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman-Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental-quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.
- Roesel, Arend F.,Ugandi, Mihkel,Huyen, Nguyen Thi Thu,Májek, Michal,Broese, Timo,Roemelt, Michael,Francke, Robert
-
p. 8029 - 8044
(2020/07/25)
-
- AlCl3-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides
-
AlCl3-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides was developed, which represents an effective synthesis of S-aryl thiocarbamates via C-S bond formation reaction.
- Chen, Jie,Mao, Jincheng,He, Yue,Shi, Daqing,Zou, Binyang,Zhang, Guoqi
-
supporting information
p. 9496 - 9500
(2015/11/18)
-
- The Newman-Kwart rearrangement re-evaluated by microwave synthesis
-
The Newman-Kwart rearrangement (NKR) has been re-evaluated by microwave heating. Microwave technology has proven to be ideal for investigating this high temperature rearrangement and facilitated the confirmation of many aspects of this valuable reaction.
- Moseley, Jonathan D.,Sankey, Rosalind F.,Tang, Olivier N.,Gilday, John P.
-
p. 4685 - 4689
(2007/10/03)
-
- β-D-phenylthioxylosides, their method of preparation and their use as therapeutic agents
-
The present invention relates, by way of novel industrial products, to the β-D-phenylthioxyloside compounds of the formula STR1 in which: X represents a sulfur atom or an oxygen atom; R1, R2 and R3, which are identical or different, each represent a hydrogen atom, a nitro group, a cyano group, a group --CO--R (in which R represents a C1 -C4 alkyl group or a trifluoromethyl group), an amino group, an acetamido group (NHCOCH3), a C1 -C4 alkoxy group, a trifluoromethyl group or a phenyl group substituted by one or more cyano, nitro or trifluoromethyl groups, it being possible for R1 and R2, taken together, to form, with the phenyl group to which they are bonded, a β-naphthalenyl group which is unsubstituted or substituted by one or more cyano, nitro or trifluoromethyl groups; and Y represents the hydrogen atom or an aliphatic acyl group. These compounds are useful as therapeutic agents, especially as venous antithrombotics.
- -
-
-