134362-34-8Relevant articles and documents
Synthesis of Enantiopure Unnatural Amino Acids by Metallaphotoredox Catalysis
Agejas, Javier,Barberis, Mario,De Frutos, Oscar,Faraggi, Tomer M.,García-Cerrada, Susana,MacMillan, David W. C.,Mateos, Carlos,Rincón, Juan A.,Rouget-Virbel, Caroline
, p. 1966 - 1973 (2021/08/18)
We describe herein a two-step process for the conversion of serine to a wide array of optically pure unnatural amino acids. This method utilizes a photocatalytic cross-electrophile coupling between a bromoalkyl intermediate and a diverse set of aryl halides to produce artificial analogues of phenylalanine, tryptophan, and histidine. The reaction is tolerant of a broad range of functionalities and can be leveraged toward the scalable synthesis of valuable pharmaceutical scaffolds via flow technology.
Evidence for the role of tetramethylethylenediamine in aqueous negishi cross-coupling: Synthesis of nonproteinogenic phenylalanine derivatives on water
Ross, Andrew J.,Dreiocker, Frank,Schae Fer, Mathias,Oomens, Jos,Meijer, Anthony J.H.M.,Pickup, Barry T.,Jackson, Richard F.W.
scheme or table, p. 1727 - 1734 (2011/05/30)
The structure of the alkylzinc-tetramethylethylenediamine (TMEDA) cluster cation 3 has been determined in the gas phase by a combination of tandem mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and DFT calculations. Both sets of experimental results establish the existence of a strongly stabilizing interaction of TMEDA with the zinc cation. High-level DFT calculations on the alkylzinc-TMEDA cluster cation 3 allowed the identification of two low energy conformers, each featuring a four-coordinate zinc atom with a bidentate TMEDA ligand, and internal coordination from the carbonyl group of the Boc group to zinc. The experimental IRMPD spectrum is reproduced with an appropriately weighted combination of the IR spectra of the two conformers identified by theory. DFT calculations on the structure of the alkylzinc halide 2 with coordinated TMEDA using the PCM model of water solvent suggest that TMEDA can promote ionization of the zinc-iodine bond in organozinc iodides under aqueous conditions, providing a credible explanation for the role of TMEDA in stabilizing the carbon-zinc bond. Reaction of the serine-derived iodide 1 with aryl iodides "on water", promoted by nano zinc in the presence of PdCl2 (Amphos) 2 (5 mol %) and TMEDA, leads to the formation of protected phenylalanine derivatives 4 in reasonable yields. In the case of ortho-substituted aryl iodides and aryl iodides that are solids at room temperature, conducting the reaction at 65°C gives improved results. In all cases, the product 5 of reductive dimerization of the iodide 1 is also isolated.
FLUORINATION OF ORGANIC COMPOUNDS
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Page/Page column 117; 118, (2010/07/10)
Methods for fluorinating organic compounds are described herein.