7391-31-3Relevant academic research and scientific papers
Asymmetric Transfer Hydrogenation of α-Substituted-β-Keto Carbonitriles via Dynamic Kinetic Resolution
Wang, Fangyuan,Yang, Tilong,Wu, Ting,Zheng, Long-Sheng,Yin, Congcong,Shi, Yongjie,Ye, Xiang-Yu,Chen, Gen-Qiang,Zhang, Xumu
supporting information, p. 2477 - 2483 (2021/02/16)
A catalytic protocol for the enantio- and diastereoselective reduction of α-substituted-β-keto carbonitriles is described. The reaction involves a DKR-ATH process with the simultaneous construction of β-hydroxy carbonitrile scaffolds with two contiguous stereogenic centers. A wide range of α-substituted-β-keto carbonitriles were obtained in high yields (94%-98%) and excellent enantio- and diastereoselectivities (up to >99% ee, up to >99:1 dr). The origin of the diastereoselectivity was also rationalized by DFT calculations. Furthermore, this methodology offers rapid access to the pharmaceutical intermediates of Ipenoxazone and Tapentadol.
Reductive C?C Coupling from α,β-Unsaturated Nitriles by Intercepting Keteniminates
Hale, Lillian V. A.,Sikes, N. Marianne,Szymczak, Nathaniel K.
supporting information, p. 8531 - 8535 (2019/05/21)
We present an atom-economic strategy to catalytically generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,β-unsaturated nitriles to a pincer-based Ru?H complex affords structurally characterized κ-N-coordinated keteniminates by selective 1,4-hydride transfer. When generated in situ under catalytic hydrogenation conditions, electrophilic addition to the keteniminate was achieved using anhydrides to provide α-cyanoacetates in high yields. This work represents a new application of hydrogen transfer catalysis using α,β-unsaturated nitriles for reductive C?C coupling reactions.
An expeditious method to synthesize difluoroboron complexes of β-keto amides from β-keto nitriles and BF3·OEt2
Xu, Chuangchuang,Xu, Jiaxi
, p. 6375 - 6383 (2017/08/16)
A convenient and expeditious strategy to synthesize difluoroboron complexes of β-keto amides has been developed from β-keto nitriles and BF3·OEt2. BF3·OEt2 serves as both a BF2 source and a Lewis acid catalyst in the synthetic strategy. The formation mechanism of the difluoroboron complexes from β-keto nitriles and BF3·OEt2 was proposed. The difluoroboron complexes can be further converted into β-keto amides by treatment with sodium acetate. The strategy features advantages such as a wide substrate scope, non-metal catalysis, and easy operation. Some of the difluoroboron complexes display good fluorescence properties in the solid state and potential application in solid-state luminescent materials.
Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β-Ketonitrile Derivatives
Kiyokawa, Kensuke,Nagata, Takaya,Minakata, Satoshi
supporting information, p. 10458 - 10462 (2016/08/24)
The highly efficient electrophilic cyanation of boron enolates using readily available cyanating reagents, N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) and p-toluenesulfonyl cyanide (TsCN), is reported. Various β-ketonitriles were prepared by this new protocol, which has a remarkably broad substrate scope compared to existing methods. The present method also allowed efficient synthesis of β-ketonitriles containing a quaternary α-carbon center. In addition, a preliminary result with the use of a chiral boron enolate for the enantioselective cyanation reaction is described.
Efficient methodology to produce a duloxetine precursor using whole cells of Rhodotorula rubra
Rimoldi, Isabella,Facchetti, Giorgio,Nava, Donatella,Contente, Martina Letizia,Gandolfi, Raffella
, p. 389 - 396 (2016/05/19)
Different types of yeasts were employed as biocatalysts in the reduction of β-ketonitriles. The red microorganism, Rhodotorula rubra, was selected as the best performing catalyst in the reduction of different substituted ketonitriles giving total stereoselectivity in most cases (90-99% ee). In particular, its use as fresh and lyophilised cells was expanded to a semi-preparative scale for the production of the duloxetine precursor 1a. R. rubra was screened in the reduction of alkylation products in comparison with Pichia henricii for assignment of configuration of products 2a and 11a after derivatisation with S-MPA.
Simple 1,3-diamines and their application as ligands in ruthenium(II) catalysts for asymmetric transfer hydrogenation of aryl ketones
Facchetti, Giorgio,Gandolfi, Raffaella,Fusè, Marco,Zerla, Daniele,Cesarotti, Edoardo,Pellizzoni, Michela,Rimoldi, Isabella
, p. 3792 - 3800 (2015/05/20)
In this research work simple unsymmetrical 1,3-diamines were studied. The synthesis of the diamines started from non-commercial available compounds. S-5a and S,S-5c were obtained by biocatalysis with non conventional yeast, Rhodotorula rubra MIM 147, with
Direct synthesis of pyrazoles from esters using tert-butoxide-assisted C-(C=O) coupling
Kim, Bo Ram,Sung, Gi Hyeon,Ryu, Ki Eun,Lee, Sang-Gyeong,Yoon, Hyo Jae,Shin, Dong-Soo,Yoon, Yong-Jin
supporting information, p. 9201 - 9204 (2015/06/08)
This paper describes the direct synthesis of pyrazoles from esters that comprises two sequential reactions: tert-butoxide-assisted C-C(=O) coupling reaction to yield β-ketonitrile or α,β-alkynone intermediates, and condensation by hydrazine addition. The method reported allows for easy control of the regioselectivity and structure of substituents at N-1, C-3, C-4 and/or C-5 positions.
Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
Nath, Dinesh,Fleming, Fraser F.
supporting information, p. 2023 - 2029 (2013/03/14)
Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in
Synthesis of β-ketonitriles, α,β-alkynones and biscabinols from esters using tert-butoxide-assisted C(=O)-C (i.e., acyl-C) coupling under ambient conditions
Kim, Bo Ram,Lee, Hyung-Geun,Kang, Seung-Beom,Jung, Kwang-Ju,Sung, Gi Hyeon,Kim, Jeum-Jong,Lee, Sang-Gyeong,Yoon, Yong-Jin
, p. 10331 - 10336 (2013/11/19)
We demonstrated the synthesis of β-ketonitriles, α,β- alkynones, and biscarbinols using tert-butoxide-assisted C(CO)-C (i.e., acyl-C) coupling of esters under ambient conditions. tert-Butoxide-assisted C(CO)-C (i.e., acyl-C) coupling of esters with cyanomethylenes and acetylenes under transition metal-free ambient conditions gives β-ketonitriles, α,β-alkynones and/or aryl bis(phenylethynyl)carbinols in moderate-to-good yields. It is noteworthy that this is a rapid, facile, and efficient process under ambient conditions, and use of cheap and stable starting materials.
Biocatalytic synthesis towards both antipodes of 3-hydroxy-3-phenylpropanitrile a precursor to fluoxetine, atomoxetine and nisoxetine
Hammond, Richard J.,Poston, Benjamin W.,Ghiviriga, Ion,Feske, Brent D.
, p. 1217 - 1219 (2007/10/03)
The bakers' yeast reduction of 3-oxo-3-phenylpropanenitrile (1) has been difficult to achieve due to a dominant alkylating mechanism. A library of 20 bakers' yeast reductases, that are overexpressed in Escherichia coli, were screened against (1). Four enzymes were found to reduce this substrate and by varying the enzyme both enantiomers of 3-hydroxy-3-phenylpropanitrile (2) could be prepared with a high enantiomeric excess. In addition, the Escherichia coli whole-cell system can be optimized to nearly eliminate the competing alkylating mechanism. By using this system, a formal biocatalytic synthesis of both antipodes of fluoxetine, atomoxetine and nisoxetine has been demonstrated.
