Gavrilov, Vladislav K

Gavrilov K., Chuchelkin I., Firsin I., Trunina V., Gavrilov V., Zheglov S., Fedorov D., Tafeenko V., Zamilatskov I., Zimarev V., Goulioukina N.S.

A series of easy-to-prepare and modular chiral P,S-bidentate phosphoramidites were synthesized. With respect to Pd(II), these ligands showed the ability to form stable P,S-chelate allylic complexes. The structures of the...

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Firsin I.D., Trunina V.M., Shiryaev A.A., Shkirdova A.O., Bermesheva E.V., Tafeenko V.A., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Zheglov S.V., Firsin I.D., Trunina V.M., Borisova N.E., Bityak Y.P., Maloshitskaya O.A., Tafeenko V.A., Zimarev V.S., Goulioukina N.S.

A series of structurally diverse diamidophosphite-sulfides were synthesized from 1,2-thioether alcohols. With respect to Pd(II), these hemilabile ligands showed the ability to form both P,S-chelates and complexes with two ligands connected to the metal P-monodentately. The structures of the ligands and complexes were confirmed by two-dimensional (2D) NMR spectroscopy and single-crystal X-ray diffraction. These stereoselectors provided up to 98% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 78% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. Furthermore, up to 71% ee was achieved in the rare reaction between 2-(diethoxyphosphoryl)-1-phenylallyl acetate and aniline. The effects of the structural parameters, reaction conditions, and ligand-to-metal ratio on the catalytic results are discussed. Due to the ability of the ligands to form structurally different catalytic species, a pronounced dependence of the asymmetric induction on the ligand-to-metal ratio is shown.

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Trunina V.M., Firsin I.D., Zheglov S.V., Bityak Y.P., Fedorov D.A., Zimarev V.S., Goulioukina N.S.

A new P*,S-bidentate diamidophosphite ligand 1, containing a stereogenic phosphorus atom as a part of the 1,3,2-diazaphospholidine ring, was synthesized based on 3-(phenylthiomethyl)phenol. Palladium catalysts on its basis demonstrated a high enantioselectivity in the allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate (76% ee), the amination with pyrrolidine (74% ee), and the alkylation of cinnamyl acetate with ethyl 2-oxocyclohexanecarboxylate (83% ee). The reaction of ligand 1 with [Pd(allyl)Cl]2 in the presence of AgBF4 afforded a mixture of cationic palladium complexes: chelate [Pd(allyl)1]BF4 and head-to-head binuclear complex [Pd(allyl)1]2(BF4)2.

Gavrilov V.K., Chuchelkin I.V., Zheglov S.V., Gavrilov K.N., Firsin I.D., Borisova N.E.

New readily accessible aminodiol and diaminoalcohol were obtained using simple condensation and reduction reactions. On their basis, earlier unknown ligands of bicyclophosphite nature with asymmetric phosphorus atoms were synthesized.

Gavrilov K.N., Chuchelkin I.V., Trunina V.M., Gavrilov V.K., Firsin I.D., Bermesheva E.V.

A new representative of novel chiral P*, N-bidentate bicyclic phosphoramidite ligands was synthesized. Palladium catalysts based on this ligand were tested in the asymmetric allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate and in the amination of the same substrate with pyrrolidine and demonstrated high activity (up to 100% conversion) and enantioselectivity up to 40% ee.

Antuganov D., Nadporojskii M., Gavrilov V., Kondratenko Y.

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Zheglov S.V., Firsin I.D., Trunina V.M., Zamilatskov I.A., Tyurin V.S., Tafeenko V.A., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

A series of diamidophosphite ligands of various structure and denticity were synthesized from (11 S ,12 S )-bis(hydroxymethyl)-9,10-dihydro-9,10-ethanoanthracene as a “roof shape” 1,4-diol. On the basis of these ligands, we obtained three types of...

Chuchelkin I.V., Gavrilov K.N., Gavrilov V.K., Zheglov S.V., Firsin I.D., Perepukhov A.M., Maximychev A.V., Borisova N.E., Zamilatskov I.A., Tyurin V.S., Dejoie C., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

A large family of P,S-bidentate diamidophosphite ligands were readily synthesized from accessible hydroxyl-thioether compounds. One type of Pd(II) cationic allylic complex with these diamidophosphites fulfilling a P-monodentate function, and three types, where the ligands act as P,S-bridging ligands (coordination polymer and head-to-head and head-to-tail dimers), were obtained. In addition, neutral Pd(II) halide complexes were generated in situ as common intermediates for both groups of cationic dimers. The structures of the ligands and complexes were elucidated by means of 2D-NMR and were confirmed by powder X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited up to 94% ee in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl acetate with various C- and N-nucleophiles. Ee values of up to 80% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, up to 61% ee was achieved in the asymmetric amination of 2-(diethoxyphosphoryl)-1-phenylallyl acetate with aniline. The effects of the diamidophosphite and thioether moieties on the catalytic activity and enantioselectivity were investigated.

Firsin I.D., Chuchelkin I.V., Gavrilov V.K., Trunina V.M., Zimarev V.S., Zheglov S.V., Gavrilov K.N., Goulioukina N.S.

Chiral P*,S-diamidophosphites with a 1,3,2-diazaphospholidine core and exocyclic 1,2-hydroxyl-thioether fragments were prepared. These asymmetric inducers provided up to 86% ee in the Pd-catalyzed ...

Gavrilov K.N., Chuchelkin I.V., Zheglov S.V., Firsin I.D., Trunina V.M., Gavrilov V.K., Borisova N.E., Zimarev V.S., Denesh A.A., Goulioukina N.S.

The reaction of P ,S-phosphoramidite bearing ( R a )-BIPHEN H2 core and exocyclic amino sulfide as the new ligand with [Pd(ppp-allyl)Cl] 2 in the presence of AgBF 4 yielded a cationic metallochelate [Pd(ppp-allyl)(L)]BF 4 . This new chiral inducer provided up to 90% ee in the Pd-mediated allylic substitution reaction of ( E )-1,3-diphenylallyl acetate with various C- and N-nucleophiles. In the Pd-catalyzed amination of 2-diethoxyphosphoryl-1-phenylallyl acetate with aniline, ee values up to 57% were achieved.

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Zheglov S.V., Firsin I.D., Trunina V.M., Maximychev A.V., Perepukhov A.M.

New bis(diamidophosphite) ligand with stereogenic phosphorus atoms in the 1,3,2-diaza-phospholidine rings was synthesized based on (1R,2R)-[N, N′-bis(3-hydroxybenzylidene)]-1,2-diaminocyclohexane. This ligand provided up to 73% ee in Pd-catalyzed asymmetric allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate and up to 80% ee in its amination with pyrrolidine, with the starting substrate conversion being quantitative.

Gavrilov K.N., Chuchelkin I.V., Zimarev V.S., Zheglov S.V., Gavrilov V.K., Firsin I.D., Maximychev A.V., Perepukhov A.M., Chernyshev V.V., Goulioukina N.S.

Two novel diastereomeric P∗,N,S-diamidophosphite ligands of the 1,3,2-diazaphospholidine series bearing a ferrocene moiety were synthesized in good yield. The use of these enantiopure ligands in the Pd-catalyzed allylic substitution of (E)-1,3-diphenylallyl acetate with CH2(CO2Me)2 and (CH2)4NH provided products with high enantiomeric excesses (up to 93% and 85% ee). Ee values up to 73% and 60% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate or ethyl 2-acetamido-3-oxobutanoate, respectively. The efficiencies of the diastereomeric stereoselectors were compared.

Chuchelkin I.V., Gavrilov K.N., Borisova N.E., Perepukhov A.M., Maximychev A.V., Zheglov S.V., Gavrilov V.K., Firsin I.D., Zimarev V.S., Mikhel I.S., Tafeenko V.A., Murashova E.V., Chernyshev V.V., Goulioukina N.S.

Novel diamidophosphites based on β-hydroxyamides were prepared, and their individual and in situ formed complexes were tested in Pd-mediated allylations.

Gavrilov K.N., Chuchelkin I.V., Zheglov S.V., Firsin I.D., Zimarev V.S., Gavrilov V.K., Maximychev A.V., Perepukhov A.M., Goulioukina N.S.

A novel P*,S-bidentate diamidophosphite ligand with a 1,3,2-diazaphospholidine core and an exocyclic thioether fragment provided up to 86% ee in the Pd-catalyzed alkylation of rac-(E)-1,3-diphenylallyl acetate with dimethyl malonate, as well as up to 73 and 75% ee in the amination of this substrate with pyrrolidine and diethyl (aminomethyl)phosphonate, respectively. For the Pd-catalyzed alkylation of cinnamyl acetate with β-keto esters, ee values up to 76% were achieved.

Nguyen H.H., Adhikary S.D., Chang Y.C., Zotor P., Jeon J.

Debnath S., Giri S., Mani G.

The contrasting reactions of a series of new bis(thioether) molecules with nickel salts have led to synthetic methods selective for particular toroidal nickel(ii) thiolates by the C–S bond cleavage with X-ray structures and DFT study.

Romero-Chávez M.M., Macías-Hernández C.E., Ramos-Organillo Á., Jiménez-Ruiz E.I., Robles-Machuca M., Ocaño-Higuera V.M., Sumaya-Martínez M.T.

A new family of monothiooxalamides derived from 2-aminobenzimidazole was synthesized, and their structures were confirmed by

Gavrilov K., Chuchelkin I., Firsin I., Trunina V., Gavrilov V., Zheglov S., Fedorov D., Tafeenko V., Zamilatskov I., Zimarev V., Goulioukina N.S.

A series of easy-to-prepare and modular chiral P,S-bidentate phosphoramidites were synthesized. With respect to Pd(II), these ligands showed the ability to form stable P,S-chelate allylic complexes. The structures of the...

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Firsin I.D., Trunina V.M., Shiryaev A.A., Shkirdova A.O., Bermesheva E.V., Tafeenko V.A., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.

Santos C.M., Silva A.M.

AbstractChalcones are a class of naturally occurring flavonoid compounds associated to a variety of biological and pharmacological properties. Several reviews have been published describing the synthesis and biological properties of a vast array of analogues. However, overviews on the reactivity of chalcones has only been explored in a few accounts. To fill this gap, a systematic survey on the most recent developments in the transition metal‐catalyzed transformation of chalcones was performed. The chemistry of copper, palladium, zinc, iron, manganese, nickel, ruthenium, cobalt, rhodium, iridium, silver, indium, gold, titanium, platinum, among others, as versatile catalysts will be highlighted, covering the literature from year 2000 to 2023, in more than 380 publications.

Seo S., Shin T., Choi I., Kim H.

Han L., Xu Q., Liu J., Yang Y., Liang J.

Zagidullin A., Ganushevich Y., Korchagin D.V., Lönnecke P., Hey-Hawkins E., Vasili M.

Utilizing the W(CO)5 group as a promoter, we have established a straightforward pathway for the conversion of simple 1-alkyl-1,2-diphospholes to P,P’-bidentate caged phosphines via [4+2] cycloaddition reactions. Furthermore, during the...

Gavrilov K.N., Chuchelkin I.V., Trunina V.M., Gavrilov B.K., Firsin I.D., Rud E.S., Tafeenko V.A., Bermesheva E.V.

A new representative of P*-monodentate bicyclic amidophosphite ligands of 2,6-dioxa-7-aza-1-phosphabicyclo[2.2.1]heptane series and its complex [Pd(allyl)(L)Cl] were obtained. Newly synthesized compounds were thoroughly characterized by 31P{1H}, 1H, and 13C{1H} NMR spectroscopy and 2D NMR experiments. The structure of the ligand was confirmed by X-ray diffraction analysis. Palladium catalysts derived from this chiral inductor provided up to 50% ee in asymmetric amination of (E)-1,3-diphenylallyl acetate with pyrrolidine.

Zimarev V.S., Chuchelkin I.V., Gavrilov K.N., Zamilatskov I.A., Tafeenko V.A., Lokshin B.V., Goulioukina N.S.

An unusual neutral dinuclear palladium(II) complex with two head-to-head orientated μ-P,S-bridging ligands was obtained by the reaction of Pd(MeCN)2 Cl2 with (1R,5R)-3-(4-phenylthiobutoxy)-2,4-diphenyl-2,4-diaza-3-phospha-bicyclo[3.4.0]nonane. The dimeric structure of the complex in the solid state and in solution was thoroughly confirmed using appropriate analytical techniques: single crystal X-ray diffraction analysis, HRMS, FTIR and NMR spectroscopy.

Pereira M.M., Carrilho R.M., Calvete M.J.

This chapter covers the most relevant literature published during the year 2021, related to tervalent phosphorus acid derivatives. Some of the most relevant concepts are reported, regarding synthetic methodologies to phosphorus amides (aminophosphines, phosphoramidites and diamidophosphites), phosphorus esters (phosphinites, phosphonites and phosphites), and mixed phosphorus compounds bearing two different tervalent phosphorus moieties. A critical selection of their applications is briefly assessed, with an emphasis on the catalytic applications of ligands and metal complexes.

Zhang J., Zhu W., Xiao D., Zhou P., Huang L., Liu W.

Leinauer L., Parla G., Messelbeger J., Herrera A., Heinemann F.W., Langer J., Chuchelkin I., Grasruck A., Frieß S., Chelouan A., Gavrilov K., Dorta R.

Planar chirality is introduced in a ‘privileged’ P-alkene phosphoramidite ligand and shown to overwhelm the chirality of the BINOL auxiliary.

Bellemin-Laponnaz S., Achard T.

AbstractThe ligand that stabilizes the metal center is crucial to its catalytic activity. Historically dominated by phosphorus and nitrogen, sulfur has long been little considered as a hetero element for stabilizing a potentially active metal center. However, this situation is changing and we are seeing more and more examples that incorporate this element. This review provides an overview of recent transition-metal-catalyzed reactions with ligands containing neutral sulfur groups, i.e. thioethers. A selection of examples published since 2013 illustrates the diversity of applications of thioether-containing ligands and shows that sulfur should be more widely used in the development of homogeneous catalysis.1 Introduction2 Phosphorus-Thioether Ligands3 Nitrogen-Thioether Ligands4 Oxygen-Thioether Ligands5 NHC-Thioether Ligands6 Cycloolefin-Thioether Ligands7 Conclusion

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Zheglov S.V., Firsin I.D., Trunina V.M., Borisova N.E., Bityak Y.P., Maloshitskaya O.A., Tafeenko V.A., Zimarev V.S., Goulioukina N.S.

A series of structurally diverse diamidophosphite-sulfides were synthesized from 1,2-thioether alcohols. With respect to Pd(II), these hemilabile ligands showed the ability to form both P,S-chelates and complexes with two ligands connected to the metal P-monodentately. The structures of the ligands and complexes were confirmed by two-dimensional (2D) NMR spectroscopy and single-crystal X-ray diffraction. These stereoselectors provided up to 98% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 78% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. Furthermore, up to 71% ee was achieved in the rare reaction between 2-(diethoxyphosphoryl)-1-phenylallyl acetate and aniline. The effects of the structural parameters, reaction conditions, and ligand-to-metal ratio on the catalytic results are discussed. Due to the ability of the ligands to form structurally different catalytic species, a pronounced dependence of the asymmetric induction on the ligand-to-metal ratio is shown.

Pellissier H.

This review collects the developments in the use of TADDOL-derived phosphorus ligands in asymmetric metal catalysis reported since the beginning of 2011, illustrating the power of these cheap and easily tunable ligands to promote many types of highly enantioselective transformations in the presence of a diversity of metals.

Steinlandt P.S., Zhang L., Meggers E.

Gavrilov K.N., Chuchelkin I.V., Trunina V.M., Firsin I.D., Bityak Y.P., Fedorov D.A., Zimarev V.S., Goulioukina N.S.

Abstract New P,S-bidentate phosphoramidite ligands, including these having a stereogenic phosphorus atom in the 1,3,2-dioxaphosphepine ring, have been synthesized on the basis of (Ra)-BINOL and its adamantanyl derivatives. With their participation in the Pd-catalyzed asymmetric allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate and the amination with pyrrolidine involving these ligands have afforded selectivity up to 84 and 75% ee, respectively.

Rajmane A., Kumbhar A.

• Pd catalyzed C-C and C-X cross coupling reactions. • Update of the recent efforts made in the coupling reactions by Pd complexes based on the P–N ligands. • The present part focused on the applications of the ligands containing N and P as a donor atoms. In recent years, Pd-catalyzed cross-coupling reactions have been used widely as expeditious reactions in various fields of chemistry. Traditionally, these cross-coupling reactions have been carried out by using different phosphine ligands. Though the phosphine ligands have been extensively used, they suffer from many limitations like poor air, moisture, and thermal stability. Hence, in recent years phosphine-free ligands such as N-heterocyclic carbenes and amines have attracted countless attention in the field of catalysis. Unfortunately, the ligands having only N as a donor atom can activate aryl iodides and bromides, while aryl chlorides are less reactive. Hence, the P–N ligands containing functional moiety, with donor N or P atom have been prepared and used for different organic transformations. An even more effective mixed donor P, N-ligands have many advantages in asymmetric catalysis because of the distinctly different characteristics like a ‘soft’ P-ligand as a π-acceptor and a ‘hard’ N-ligand as a σ-donor. This compressive review highlights the results of the highly active ligands and complexes containing N in combination with P as a donor atom.

Gonchar M.R., Ninin F.S., Milaeva E.R., Nazarov A.A.

New organometallic ruthenium complexes with glucose-based phosphite ligands bearing uracil, thymine, and 5-fluorouracil units as well as the bromide and iodide ligands were synthesized. Compounds bearing the bromide and iodide ligands were found to be more hydrolytically stable than their chloro counterparts. Antiproliferative activity of the synthesized compounds was evaluated against several cancer cell lines. It was found that these compounds are low toxic (IC50 > 100 μmol L−1) and their antiproliferative activity is independent of the nature of the halogen in their structure.

Shamsiev R.S., Egiazaryan K.T., Flid V.R.

The formation of products of oxidative and reductive allylation of norbornadiene by allyl formate (AF) in the presence of Pd0 triphenylphosphine complexes was modeled by the PBE/L11 method in terms of the density functional theory. According to calculations of all most probable routes to the norbornadiene allylation products, the highest energy barriers correspond to the transition state of formation of the first C-C bond. Two complexes, Pd(AF)(PPh3)2 and Pd(AF)(PPh3), can be treated as catalytically active ones. The PPh3 ligands cause a 7.6–8.2 kcal mol−1 decrease in the activation barriers to the formation of the second C-C bond necessary to generate the products of oxidative allylation of norbornadiene. The formation of 5-methylene-6-vinylbicyclo[2.2.1]-hept-2-ene proceeds via opening of the cyclobutane ring.

Shi B., Liu J., Wang Z., Wang L., Lan Y., Lu L., Xiao W.

Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd-catalyzed asymmetric [3+2] annulation with enyne-Cope rearrangement, providing a facile route to chiral 9-membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central-to-axial chirality transfer.

Shi B., Liu J., Wang Z., Wang L., Lan Y., Lu L., Xiao W.

Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd-catalyzed asymmetric [3+2] annulation with enyne-Cope rearrangement, providing a facile route to chiral 9-membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central-to-axial chirality transfer.

Sen A., Kumar R., Pandey S., Vipin Raj K., Kumar P., Vanka K., Chikkali S.H.

Synthesis of hybrid phosphorus ligands is a multistep, time-consuming exercise. This limitation has been addressed by meticulous understanding of the process of formation of hybrid ligands and a one pot synthesis of a phosphine-phosphite ligand (L1) is reported for the first time. L1 coordinates to Rh and catalyzes asymmetric hydrogenation of 15 substrates with a high TOF of 2289 and enantiomeric excess of 92 %.

Gavrilov K.N., Chuchelkin I.V., Gavrilov V.K., Zheglov S.V., Firsin I.D., Trunina V.M., Zamilatskov I.A., Tyurin V.S., Tafeenko V.A., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

A series of diamidophosphite ligands of various structure and denticity were synthesized from (11 S ,12 S )-bis(hydroxymethyl)-9,10-dihydro-9,10-ethanoanthracene as a “roof shape” 1,4-diol. On the basis of these ligands, we obtained three types of...

Margalef J., Biosca M., de la Cruz Sánchez P., Faiges J., Pàmies O., Diéguez M.

• Helping in the sustainable production of fine chemicals through an appropriate design of M-heterodonor P-N/O/S catalysts. • Efficient metal-containing heterodonor P-N/O/S catalysts for asymmetric reactions. • Modular and readily accessible heterodonor ligands built up with a broad applicability. The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either the ligand backbone, the electronic and/or steric properties of the phosphine group or by exchanging the phosphine to a phosphinite or a phosphite group. In this respect, the structures of chiral P-oxazoline ligands have become more diverse and new families of very efficient ligands have emerged, which have improved catalytic performance in some asymmetric transformations, with an increased versatility, both in the range of reactions and in the range of substrates/reagents. In addition, most of ligands are synthesized from easily accessible chiral amino alcohols, maintaining the short and efficient synthetic route developed for PHOX ligands. New ligands have been developed by replacing the oxazoline functionality with several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., and O- and S-groups. This review offers a critical overview of the utility of these most successful bidentate heterodonor P-N, P-O and P-S ligand families applied in metal-mediated processes. We illustrate how, through proper ligand design, these heterodonor bidentate ligand families can be an excellent source of ligands, with superior catalytic performance in many asymmetric reactions than the best C 2 -symmetric N,N and P,P-ligands reported so far.

Chuchelkin I.V., Gavrilov K.N., Gavrilov V.K., Zheglov S.V., Firsin I.D., Perepukhov A.M., Maximychev A.V., Borisova N.E., Zamilatskov I.A., Tyurin V.S., Dejoie C., Chernyshev V.V., Zimarev V.S., Goulioukina N.S.

A large family of P,S-bidentate diamidophosphite ligands were readily synthesized from accessible hydroxyl-thioether compounds. One type of Pd(II) cationic allylic complex with these diamidophosphites fulfilling a P-monodentate function, and three types, where the ligands act as P,S-bridging ligands (coordination polymer and head-to-head and head-to-tail dimers), were obtained. In addition, neutral Pd(II) halide complexes were generated in situ as common intermediates for both groups of cationic dimers. The structures of the ligands and complexes were elucidated by means of 2D-NMR and were confirmed by powder X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited up to 94% ee in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl acetate with various C- and N-nucleophiles. Ee values of up to 80% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, up to 61% ee was achieved in the asymmetric amination of 2-(diethoxyphosphoryl)-1-phenylallyl acetate with aniline. The effects of the diamidophosphite and thioether moieties on the catalytic activity and enantioselectivity were investigated.

Cabré A., Verdaguer X., Riera A.

Chiral amines are key structural motifs present in a wide variety of natural products, drugs, and other biologically active compounds. During the past decade, significant advances have been made with respect to the enantioselective synthesis of chiral amines, many of them based on catalytic asymmetric hydrogenation (AH). The present review covers the use of AH in the synthesis of chiral amines bearing a stereogenic center either in the α, β, or γ position with respect to the nitrogen atom, reported from 2010 to 2020. Therefore, we provide an overview of the recent advances in the AH of imines, enamides, enamines, allyl amines, and N-heteroaromatic compounds.

Firsin I.D., Chuchelkin I.V., Gavrilov V.K., Trunina V.M., Zimarev V.S., Zheglov S.V., Gavrilov K.N., Goulioukina N.S.

Chiral P*,S-diamidophosphites with a 1,3,2-diazaphospholidine core and exocyclic 1,2-hydroxyl-thioether fragments were prepared. These asymmetric inducers provided up to 86% ee in the Pd-catalyzed ...