851615-07-1Relevant articles and documents
Novel Axially Chiral Ligand-Enabled Copper-Catalyzed Asymmetric Oxidative Coupling of 2-Naphthols for the Synthesis of 6,6′-Disubstituted BINOLs
Wang, Pengyang,Cen, Shouyi,Gao, Jun,Shen, Ahui,Zhang, Zhipeng
, p. 2321 - 2326 (2022/04/07)
Novel axially chiral ligands have been designed and synthesized by merging the chelating picolinic acid with substituted BINOLs. The in-situ-prepared copper catalysts from the ligands and CuI enable the asymmetric oxidative coupling of 2-naphthols, afford
An Iridium Catalytic System Compatible with Inorganic and Organic Nitrogen Sources for Dual Asymmetric Reductive Amination Reactions
Chang, Mingxin,Gao, Zhaofeng,Geng, Huiling,Huang, Haizhou,Liu, Jingwen
, p. 27307 - 27311 (2021/11/17)
Asymmetric reductive amination (ARA) is one of the most promising methods for the synthesis of chiral amines. Herein we report our efforts on merging two ARA reactions into a single-step transformation. Catalyzed by a complex formed from iridium and a steric hindered phosphoramidite, readily available and inexpensive aromatic ketones initially undergo the first ARA with ammonium acetate to afford primary amines, which serve as the amine sources for the second ARA, and finally provide the enantiopure C2-symmetric secondary amine products. The developed process competently enables the successive coupling of inorganic and organic nitrogen sources with ketones in the same reaction system. The Br?nsted acid additive plays multiple roles in this procedure: it accelerates the formation of imine intermediates, minimizes the inhibitory effect of N-containing species on the iridium catalyst, and reduces the primary amine side products.
Fast, Efficient and Low E-Factor One-Pot Palladium-Catalyzed Cross-Coupling of (Hetero)Arenes
Pinxterhuis, Erik B.,Visser, Paco,Esser, Iwan,Gualtierotti, Jean-Baptiste,Feringa, Ben L.
supporting information, p. 9452 - 9455 (2017/10/23)
The homocoupling of aryl halides and the heterocoupling of aryl halides with either aryl bromides or arenes bearing an ortho-lithiation directing group are presented. The use of a Pd catalyst, in combination with t-BuLi, allows for the rapid and efficient formation of a wide range of polyaromatic compounds in a one pot procedure bypassing the need for the separate preformation of an organometallic coupling partner. These polyaromatic structures are obtained in high yields, in 10 min at room temperature, with minimal waste generation (E-factors as low as 1.5) and without the need for strict inert conditions, making this process highly efficient and practical in comparison to classical methods. As illustration, several key intermediates of widely used BINOL-derived structures are readily prepared.
Expedient BINOL derivative arylations
Albini, Mathieu,Taillier, Catherine,Dalla, Vincent,Blanchet, Jér?me,Rouden, Jacques
, p. 6420 - 6422 (2014/12/10)
A dramatic improvement of our previous methodology based on a Suzuki-Miyaura cross-coupling to access 3,3′-disubstituted H8-BINOLs using microwave heating is reported herein. These new conditions represent a large gain in term of atom-economy, reaction time, catalyst loading, and excess of reagents employed.
Rapid synthesis of 3,3′ bis-arylated BINOL derivatives using a C-H borylation in situ suzuki-miyaura coupling sequence
Ahmed, Ijaz,Clark, Daniel A.
supporting information, p. 4332 - 4335 (2014/10/16)
The increased interest in BINOL derived catalysts for asymmetric transformations has encouraged us to disclose a rapid and scalable method of preparing 3,3′ bis-arylated BINOL derivatives 1 using a one-pot CH borylation/Suzuki-Miyaura coupling sequence. T
Synthesis and structural aspects of N-triflylphosphoramides and their calcium salts'highly acidic and effective Bronsted acids
Rueping, Magnus,Nachtsheim, Boris J.,Koenigs, Rene M.,Ieawsuwan, Winai
scheme or table, p. 13116 - 13126 (2011/02/24)
Recently, 1,1′-bi-2-naphthol (BINOL)-based N-triflylphosphoramides emerged as a new class of potent Bronsted acid catalysts. In this paper we describe the efficient synthesis of various BINOL-based N- triflylphosphoramides and their calcium salts. Furthermore, X-ray crystal structure analysis combined with energy-dispersive X-ray spectroscopy (EDX) measurements confirmed that the synthesised chiral N-triflylphosphoramides are highly acidic metal-free catalysts. Freedom! The synthesis and structure determination of various 1,1′-bi-2-naphthol (BINOL)-based N-triflylphosphoramides and their corresponding calcium salts is presented. A simple acidic treatment of the calcium salts provides the metal-free Bronsted acids (see scheme; Tf=trifluoromethanesulfonyl).
Facile and efficient enantioselective strecker reaction of ketimines by chiral sodium phosphate
Shen, Ke,Liu, Xiaohua,Cai, Yunfei,Lin, Lili,Feng, Xiaoming
supporting information; scheme or table, p. 6008 - 6014 (2010/02/28)
A facile and efficient enantioselective Strecker reaction of ketimines catalyzed by a chiral alkali-metal salt has been developed. When 10 mol% BNPNa (BNP=1,1'-binaphthyl-2,2'-diylphosphate) prepared in situ and 10 mol% para-tert-butylortho-adamantylphenol (PBAP) were introduced into the reaction, up to 96% yield and up to 95% ee (ee=enantiomeric excess) were obtained. Both aliphatic and aromatic ketimines, especially sterically bulky cyclic ketimines derived from β-acetonaphthone, α-indanone, and α-tetralone were found suitable for this reaction. On the basis of the experimental results and previous reports, trimethylsilyl cyanide (TMSCN) was indicated to be the real reactive nucleophile despite the existence of PBAP, and a possible working model was proposed to explain the origin of the asymmetric induction. The facile availability of 1,1'-binaphthyl-2,2'-diylphosphoric acid (BNPH) and the simplicity of the procedure are beneficial for practical applications.
