33641-42-8Relevant articles and documents
Trideuteromethylation Enabled by a Sulfoxonium Metathesis Reaction
Shen, Zuyuan,Zhang, Shilei,Geng, Huihui,Wang, Jiarui,Zhang, Xinyu,Zhou, Anqi,Yao, Cheng,Chen, Xiaobei,Wang, Wei
supporting information, p. 448 - 452 (2019/01/14)
A conceptually novel sulfoxonium metathesis reaction between TMSOI and cost-effective DMSO-d6 is developed for the efficient generation of a new trideuteromethylation reagent TDMSOI. The new reagent TDMSOI is produced highly efficiently by simply heating a mixture of TMSOI and DMSO-d6 and directly used for subsequent trideuteromethylation in a "one-pot" operation. The preparative power of the new versatile reagent and the "one-pot" protocol is demonstrated by its use to install the ?CD3 moiety into broad functionalities including phenols, thiophenols, acidic amines, and enolizable methylene units in high yield and at a useful level of deuteration (>87% D).
Tuning the lewis acidity of boranes in frustrated lewis pair chemistry: Implications for the hydrogenation of electron-poor alkenes
Nicasio, Juan A.,Steinberg, Sebastian,Ines, Blanca,Alcarazo, Manuel
, p. 11016 - 11020 (2013/09/02)
An analysis of the metal-free reduction of electron deficient olefins by frustrated Lewis pairs indicates that the rate-determining step might be either the heterolytic cleavage of H2 to form an -onium borohydride salt, or the subsequent transfer of the hydride moiety to the substrate following a Michael-type addition reaction. While the use of strong Lewis acids such as B(C6F5)3 facilitates the first of these processes, hydride transfer to the olefin should be contrarily favoured by the use of weak Lewis acids which, for this very same reason, might be unable to promote the prior H2 split. After systematic testing of several boranes of different Lewis acidity (assessed by using the Childs' method) and steric demand, an optimal situation that employs tris(2,4,6-trifluorophenyl) borane was reached. Mixtures of this borane with 1,4-diazabicyclo[2.2.2]octane (DABCO) exhibited excellent catalytic activity for the hydrogenation of alkylidene malonates. In fact, this transformation could be achieved under milder conditions than those we reported previously. Moreover, the reaction scope could be expanded to other electron deficient olefins containing esters, sulfones or nitro functionalities as electron-withdrawing substituents.
NUCLEOPHILIC ADDITION TO STYRYL SULPHONES. PART I. A STUDY ON THE REGIOCHEMISTRY.
Benedetti, F.,Fabrissin, S.,Risaliti, A.
, p. 3887 - 3894 (2007/10/02)
Styryl sulphones undergo nucleophilic addition, with the nucleophile adding at the α- or the β-position, with respect to the sulphone group; β-attack is normally favoured over α-attack.Factors which can change the regioselectivity in favour of the addition of the nucleophile to the α-position are discussed for heteronucleophiles as well as carbon nucleophiles.
