Synthesis and applications of high-performance P-chiral phosphine ligands

Imamoto, Tsuneo

doi:10.2183/pjab.97.026

Cited by 30 publications

(21 citation statements)

References 137 publications

(111 reference statements)

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“…Organophosphorus compounds bearing P-stereogenic centers have widely emerged in biological molecules and natural products ( Figure 1A )( Kolodiazhnyi, 2021 ), and they also serve as broadly useful ligands and catalysts in asymmetric synthesis ( Dutartre et al, 2016 ; Xu et al, 2019 ; Imamoto, 2021 ) ( Figure 1B ). Nowadays, P-stereogenic scaffolds show an increasing presence in bioactive molecules for medical uses ( Figure 1C ).…”

Section: Introductionmentioning

confidence: 99%

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Liu

Chen²,

Wang³

et al. 2023

Front. Chem.

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P-chirality broadly appears in natural and synthetic functional molecules. The catalytic synthesis of organophosphorus compounds bearing P-stereogenic centers is still challenging, due to the lack of efficient catalytic systems. This review summarizes the key achievements in organocatalytic methodologies for the synthesis of P-stereogenic molecules. Different catalytic systems are emphasized for each strategy class (desymmetrization, kinetic resolution, and dynamic kinetic resolution) with examples cited to illustrate the potential applications of the accessed P-stereogenic organophosphorus compounds.

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Section: Introductionmentioning

confidence: 99%

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Liu

Chen²,

Wang³

et al. 2023

Front. Chem.

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“…The chiral center of molecules and complexes can be any atom, such as carbon, nitrogen, phosphorous, or sulfur, having four different substituents that are spatially fixed. [2][3][4][5] Tertiary amines with three different substituents are chiral when their lone pair is considered as the fourth substituent. Under normal conditions the nitrogen lone pair undergoes very fast umbrella-like inversion, [6] rendering such tertiary amines effectively racemic and enantiomer separation impossible.…”

Section: Introductionmentioning

confidence: 99%

Linearbis‐Coordinate Silver(I) and Iodine(I) Complexes with R₃R₂R₁N Tertiary Amines

Kumar,

Komulainen,

Frontera

et al. 2023

Chemistry A European J

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Homoleptic [L–I–L]⁺ iodine(I) complexes (where L is a R3R2R1N tertiary amine) were synthesized via the [L–Ag–L]⁺ → [L–I–L]⁺ cation exchange reaction. In solution, the amines form [R3R2R1N‐Ag‐NR1R2R3]⁺ silver(I) complexes, which crystallize out from solution as the meso‐[L–Ag–L]+complexes, as characterized by X‐ray crystallography. The subsequent [L–I–L]⁺ iodine(I) analogues were extremely reactive and could not be isolated in the solid state. Density Functional Theory (DFT) calculations were performed to study the Ag⁺–N and I⁺–N interaction energies in silver(I) and iodine(I) complexes, with the former ranging from ‐80 to ‐100 kJmol‐1 and latter from ‐260 to ‐279 kJmol‐1. The X‐ray crystal structures revealed Ag+···Cπ and Ag+···H–C short contacts between the silver(I) cation and flexible N‐alkyl/N‐aryl groups, which are the first of their kind in such precursor complexes.

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“…Although the stereoselective synthesis of P-chirogenic phosphorus compounds was generally carried out in a tetracoordinated series, the use of borane in phosphorus chemistry allowed significant development because sec -phosphine-boranes 3 or phosphinous derivatives 4 are easily handled and give numerous clean reactions. , In addition, the decomplexation of borane from a P-chirogenic phosphorus moiety can be easily achieved with amines, strong acids, or EtOH to afford the corresponding P(III)-compounds with complete retention of configuration. , …”

Section: Introductionmentioning

confidence: 99%

P(III)-Chirogenic Phosphinite Building Blocks by Stereospecific N→O Phosphinyl Migration

Jaillet,

Bayardon,

Rousselin

et al. 2023

J. Org. Chem.

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In the recent past, the chirality borne by a phosphorus center has aroused growing interest in many fields, and the development of new methodologies, notably using inexpensive reagents and simple experimental conditions, has become topical. An efficient stereoselective synthesis of P-chirogenic phosphinites useful as chiral phosphorus building blocks is herein described thanks to a new intramolecular phosphorus rearrangement based on P*(III)-phosphinyl N→O migration. This rearrangement was performed by heating at 50 °C aminophosphine-boranes, easily prepared from chiral amino alcohols, with DABCO in toluene overnight. Twenty-seven P-chirogenic phosphinites and borane complexes were thus prepared in yields up to 89%. The crude P*(III)-phosphinites were in situ used in stereoselective synthesis of P-chirogenic aminophosphine-phosphinites, phosphinothioates, sec-and tert-phosphine-oxides, and mono-and diphosphines in overall yields ranging from 28 to 89% and with e.e. up to 99%. Twenty-one X-ray structures of P-chirogenic compounds were established, allowing us to attribute undoubtedly their absolute configuration and the stereochemistry of the reactions. Finally, new ferrocenyl-bridged diphosphine ligands synthesized from P*(III)-chirogenic diphosphinites were tested in asymmetric metal-catalyzed reactions, providing enantioselectivities up to 95% e.e. in allylation of α-naphthylmethylamine at room temperature. To conclude, this rearrangement opens up an efficient new way for the stereoselective synthesis of numerous classes of P-chirogenic phosphorus compounds, notably bearing bulky substituents.

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Synthesis and applications of high-performance P-chiral phosphine ligands

Cited by 30 publications

References 137 publications

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Linearbis‐Coordinate Silver(I) and Iodine(I) Complexes with R₃R₂R₁N Tertiary Amines

P(III)-Chirogenic Phosphinite Building Blocks by Stereospecific N→O Phosphinyl Migration

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Synthesis and applications of high-performance P-chiral phosphine ligands

Cited by 30 publications

References 137 publications

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Organocatalytic asymmetric synthesis of P-stereogenic molecules

Linearbis‐Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines

P(III)-Chirogenic Phosphinite Building Blocks by Stereospecific N→O Phosphinyl Migration

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Product

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Linearbis‐Coordinate Silver(I) and Iodine(I) Complexes with R₃R₂R₁N Tertiary Amines