957565-66-1

Upstream product

• 99-91-2 para-chloroacetophenone 

Downstream Products

• 957565-69-4 [1-(p-chlorophenyl)-1-deuteroethyl]triphenylphosphonium bromide 

Relevant academic research and scientific papers

Highly efficient D2 generation by dehydrogenation of formic acid in D2O through H+/D+ exchange on an iridium catalyst: Application to the synthesis of deuterated compounds by transfer deuterogenation

Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D2) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H+/D+ exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D2 evolution (purity up to 89%) was achieved by using HCO2H as an electron source and D2O as a deuterium source; a rhodium analogue provided HD gas (98%) under similar conditions. Furthermore, pressurized D 2 (98%) without CO gas was generated by using DCO2D in D2O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO2H in D2O. Mechanistic studies show that the H+/D+ exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Cheap D2 gas! Convenient generation of deuterium gas (D2) and preparation of deuterated compounds on a laboratory scale are demonstrated using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'- bipyridine (see scheme). The "umpolung" of a hydrogen atom of water was achieved in consecutive reactions (cationic H+/D+ exchange reaction and anionic hydride (deuteride) transfer) under mild conditions. Copyright

Transition-Metal-Free Hydrogen Autotransfer: Diastereoselective N-Alkylation of Amines with Racemic Alcohols

A practical method for the synthesis of α-chiral amines by alkylation of amines with alcohols in the absence of any transition-metal catalysts has been developed. Under the co-catalysis of a ketone and NaOH, racemic secondary alcohols reacted with Ellman's chiral tert-butanesulfinamide by a hydrogen autotransfer process to afford chiral amines with high diastereoselectivities (up to >99:1). Broad substrate scope and up to a 10 gram scale production of chiral amines were demonstrated. The method was applied to the synthesis of chiral deuterium-labelled amines with high deuterium incorporation and optical purity, including examples of chiral deuterated drugs. The configuration of amine products is found to be determined solely by the configuration of the chiral tert-butanesulfinamide regardless of that of alcohols, and this is corroborated by DFT calculations. Further mechanistic studies showed that the reaction is initiated by the ketone catalyst and involves a transition state similar to that proposed for the Meerwein–Ponndorf–Verley (MPV) reduction, and importantly, it is the interaction of the sodium cation of the base with both the nitrogen and oxygen atoms of the sulfinamide moiety that makes feasible, and determines the diastereoselectivity of, the reaction.

Unusual reaction course of styrenes to 2-arylethyltriphenylphosphonium salts

1-Arylethyltriphenylphosphonium bromides thermally rearranged to 2-arylethyltriphenylphosphonium bromides. Direct formation of 2-arylethylphosphonium bromides was achieved by reacting styrene, HBr, and triphenylphosphine. On the other hand, thermolysis of