Chemistry of α‐Phosphanyl α‐Amino Acids

Abstract

After a short introduction on potential applications and types of phosphanyl-substituted α-amino acids the current knowledge on syntheses of acyclic and heterocyclic α-phosphanyl α-amino acids, their structural features, properties, reac-[a] and coordination compounds. Dmitry Yakhvarov is a specialist in phosphorus, physical, inorganic, coordination and organoelement chemistry, catalysis and electrochemistry. His main research interests are focused on the development of new technologies for the preparation of organophosphorus and organoelement compounds, including organometallics, by electrochemical methods based on the principles of "green chemistry". In 2016 he was awarded the honorary title of "Professor of the Russian Academy of Sciences". Joachim Heinicke studied chemistry at the Martin-Luther-University Halle and performed his PhD work under supervision of Prof. A. Tzschach. Continuing work in his group, he started besides contract research on high-purity doting compounds for electronic materials investigations on various amino-and hydroxy-functional As and P compounds, including heterocycles with dicoordinated As and P, stabilized by π-bonds. After habilitation this research was extended to silylenes and later also to germylenes and carbenes. Complex chemical and catalytic studies with o-hydroxyarylphosphanes were started after moving to the University Greifswald (1990 Docent, 1992 Professor), for some years in cooperation with Prof. Keim (Aachen). The change of the education focus to biochemistry led then to investigations on the α-phosphanyl amino acids, stimulated also by some early experiments in this direction. After retirement in 2012 he is still active to round off unpublished work. Eur. J. Inorg. Chem. 2019, 1507-1518

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

“…After 1 week, a mixture of yellow (6) and colorless (pyridinium chloride) crystals was formed, which were identified by SCXRD. Pyridinium chloride was identified by unit cell parameters (P − 1): a = 4.72 Å, b = 7.49 Å, c = 8.14 Å, α = 87.3°, β = 88.3°, γ = 87.5°, V = 287 Å 3 The mixture was stirred for 1 day at ambient temperature. Hexane was layered from the gas phase on clear yellow solution.…”

Ni-Based Complexes in Selective Ethylene Oligomerization Processes

“…Heinicke and co-workers developed a number of phosphino-amino acids, which is used as ligands of SHOP-type catalytic systems [108][109][110]. For example, α-diphenylphosphino-N-(pyrazin-2-yl)glycine (77, Figure 59) in composition with Ni(COD) 2 , where COD-1,5-cyclooctadiene, oligomerizes ethylene mainly to 1-butene (24-46%) and to 1-hexene (14-26%) [111].…”

Influence of N- and P-substituents in N-aryl-phosphinoglycine ligands on the selectivity of Ni-catalysed ethylene oligomerization

“…[4][5][6][7][8][9] Such systems have been extensively modified through the use of phosphanylenolate, iminophenolate, bulky diimine, or tridentate diimine chelate ligands. [22][23][24][25][26][27][28][29] A high level of attention to these systems is largely due to the manifold possibilities in fine-tuning the properties of organometallic complexes based on trivalent phosphines. 6,7,19 Indeed, ligand tailoring is a powerful strategy in transition metal-based catalysis to initiate the process and to control selectivity.…”