51774-34-6Relevant articles and documents
Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates
Banerjee, Amit,Hattori, Tomohiro,Yamamoto, Hisashi
, (2021/06/16)
Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).
Catalytic Hydrogenation of Carboxamides with a Bifunctional Cp Ru Catalyst Bearing an Imidazol-2-ylidene with a Protic Aminoethyl Side Chain
Ikariya, Takao,Kawano, Teruhiro,Kayaki, Yoshihito,Watari, Ryo
, p. 2542 - 2547 (2019/06/08)
Synthesis of a Cp Ru complex bearing an NH 2 -functionalized N -heterocyclic carbene (C-N H) was achieved by treatment of CpRuBr(isoprene) with an equimolar amount of a silver complex, which was generated from Ag 2 O and 1-(2-aminoethyl)-3-methylimidazolium bromide, in CH 3 CN at room temperature. The new CpRuBr(C-N H) complex showed a higher catalytic performance than the related CpRuCl(P-N H) and CpRuCl(N-N H) complexes. In the reaction of N -arylcarboxamides, the amine products were obtained in satisfactory yields under mild temperature conditions.
Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium-Catalyzed Carbonylation
Domino, Katrine,Veryser, Cedrick,Wahlqvist, Benjamin A.,Gaardbo, Cecilie,Neumann, Karoline T.,Daasbjerg, Kim,De Borggraeve, Wim M.,Skrydstrup, Troels
supporting information, p. 6858 - 6862 (2018/05/08)
A palladium-catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α-bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late-stage carbon-isotope labeling.
