Efficient Oxidative Resolution of 1-Phenylphosphol-2-Ene and Diels–Alder Synthesis of Enantiopure Bicyclic and Tricyclic P-Stereogenic C-P Heterocycles

Pietrusiewicz, K. Michał; Koprowski, Marek; Drzazga, Zbigniew; Parcheta, Renata; Łastawiecka, Elżbieta; Demchuk, Oleg M.; Justyniak, Iwona

doi:10.3390/sym12030346

Cited by 6 publications

(4 citation statements)

References 67 publications

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“…Due to our previous experience, we first tried L-menthyl bromoacetate and DBTA as resolving agents. These two reagents recently allowed us to successfully resolve 1-phenylphosphol-2-ene [18,19] and secondary tert-butyl-phenylphosphine oxide [20], respectively, providing both enantiomers of the corresponding phosphine oxide of very high enantiomeric purity in a single resolution process in each case. Unfortunately, the attempted use of these reagents for the resolution of phosphinenone 2 did not result in the formation of complexes suitable for crystallization.…”

Section: Resultsmentioning

confidence: 99%

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Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (R,R)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State

et al. 2021

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The resolution of racemic 1-phenylphosphin-2-en-4-one 1-oxide (2), was achieved through the fractional crystallization of its diastereomeric complexes with (4R,5R)-(−)-2,2-dimethyl -α,α,α′,α′-tetraphenyl-dioxolan-4,5-dimethanol (R,R-TADDOL) followed by the liberation of the individual enantiomers of 2 by flash chromatography on silica gel columns. The resolution process furnished the two enantiomers of 2 of 99.1 and 99.9% e.e. at isolated yields of 62 and 59% (counted for the single enantiomer), respectively. The absolute configurations of the two enantiomers were established by means of X-ray crystallography of their diastereomerically pure complexes, i.e., (R)-2•R,R)-TADDOL and (S)-2•(R,R)-TADDOL. The structural analysis revealed that in the (R)-2•(R,R)-TADDOL complex, the P-phenyl substituent occupied a pseudoequatorial position, whereas in (S)-2•(R,R)-TADDOL, it appeared in both the pseudoequatorial and the pseudoaxial positions in four symmetrically independent molecules. Concurrent conformational changes of the TADDOL molecules were best described by the observed changes of a pseudo-torsional CO...OC angle that could be considered as a possible measure of TADDOL conformation in its receptor–ligand complexes. The structural analysis of the (R,R)-TADDOL molecule revealed that efficiency of this compound for use as an effective resolving factor comes from its ability to flexibly fit its structure to both enantiomers of a ligand molecule, producing a rare case of resolution for both pure enantiomers with one chiral separating agent. The resolved (R)-2 was used to assign the absolute configuration of a recently described (−)-1-phenylphosphin-2-en-4-one 1-sulfide by chemical correlation. In addition, an attempted stereoretentive reduction of (R)-2 by PhSiH3 at 60 °C revealed an unexpectedly low barrier for P-inversion in 1-phenylphosphin-2-en-4-one.

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Section: Resultsmentioning

confidence: 99%

“…31 P NMR (202 MHz, CDCl 3 ): δ 21.3 ppm. GCMS (EI, 70 eV) m/z = 223.05 (13), 222.05 (100), 190.10 (14), 189.10 (86), 171.10 165.05(10),(12), 143.15(12), 142.15 (96), 141.15(18), 140.05(50), 134.10 (22), 133.10 (50), 131.10 (20), 109.10 (11), 108.10 (28), 107.10 (69), 105.15 (24), 103.10 (18), 91.10 (10), 83.05 (12), 81.05 (11). Anal.…”

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confidence: 99%

Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (R,R)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State

et al. 2021

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“…It is noteworthy that phosphine oxides 2 are desired products and the olefins 5 are undesired products, in contrast to the traditional utilization of the Wittig reaction for the synthesis of olefins . The Wittig reaction has been used in the oxidative resolution of P-stereogenic tertiary phosphines. − The synthesis of phosphine oxide-based surfactants via the ring-opening Wittig olefination of a macrocyclic phosphoranylidene has also been reported …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Aryldiphenylphosphine Oxides by Quaternization of Tertiary Diphenylphosphines with Aryl Bromides Followed by the Wittig Reaction

Zhong

Huang

2020

ACS Omega

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A two-step method for the synthesis of aryldiphenylphosphine oxides from tertiary diphenylphosphines and aryl bromides is developed. The first step is the quaternization of methyldiphenylphosphine or benzyldiphenylphosphine with aryl bromides. This quaternization can be nickel-catalyzed (metal-free in some cases), and tolerate of a variety of functional groups, furnishing quaternary phosphonium salts in 48−90% yields. The second step is Wittig reactions of these quaternary phosphonium salts with furan-2-carbaldehyde or p-chlorobenzaldehyde to provide aryldiphenylphosphine oxides in 27−90% yields. The use of the Wittig reaction for the synthesis of tertiary phosphine oxides is in contrast to its traditional use for the synthesis of olefins, leaving tertiary phosphine oxide as a byproduct. This quaternization−Wittig method can be applied to synthesize aryldiphenylphosphine oxides that are difficult to access by the alkaline hydrolysis of aryltriphenylphosphonium salts, especially those bearing an electron-deficient aryl group. The ligand-coupling mechanism for the alkaline hydrolysis of (p-acylphenyl)triphenylphosphonim salts is also discussed.

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“…Cycloadditions are highly versatile reactions as a broad range of starting dienes and dienophiles (alkenes or alkynes) can be used. Additionally, they are also often highly stereoselective, providing up to four contiguous carbon stereogenic centers and opening access to other stereogenic centers as well, such as chiral phosphorus [5], thus being of paramount importance when a decrease in symmetry (i.e., increase in asymmetry) is desired or necessary as often is the case for the construction of scaffolds of many natural and related compounds. Consequently, cycloadditions provide a viable alternative to the other widespread options of preparing enantiomerically pure compounds, i.e., optical resolution [6] or application of asymmetric (auto)catalysis [7], both of these offering the possibility of enantiomeric excess amplification.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Diversity of Oxabicyclo[2.2.2]octenes Formed between Substituted 2H-Pyran-2-ones and Vinyl-Moiety-Containing Dienophiles

et al. 2020

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In Diels–Alder reactions, 2H-pyran-2-ones as dienes can yield a large variety of cycloadducts with up to four contiguous carbon stereogenic centers. Some of the potentially most useful, however difficult to prepare due to their low thermal stability, are the primary CO2-containing oxabicyclo[2.2.2]octenes, which could be formed as eight distinctive isomers (two sets of regioisomers, each of these composed of four different stereoisomers). A high-pressure synthesis of such products was recently described in a few cases where vinyl-moiety-containing dienophiles were used as synthetic equivalents of acetylene. However, structures of the primary products have been so far only rarely investigated in detail. Herein, we present seven novel single-crystal X-ray diffraction structures of such cycloadducts of both stereoisomeric forms, i.e., endo and exo. Additionally, we present a single-crystal structure of a rare case of a cyclohexadiene system stable at room temperature, obtained as a secondary product upon the retro-hetero-Diels–Alder elimination of CO2 under thermal conditions (microwave irradiation), during this elimination the symmetry is increased and out of eight initially possible isomers of the reactant, this number in the product is decreased to four. In oxabicyclo[2.2.2]octene compounds, centrosymmetric hydrogen bonding was found to be the predominant motif and diverse supramolecular patterns were observed due to rich variety of C–H⋯O and C–H⋯π interactions.

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Efficient Oxidative Resolution of 1-Phenylphosphol-2-Ene and Diels–Alder Synthesis of Enantiopure Bicyclic and Tricyclic P-Stereogenic C-P Heterocycles

Cited by 6 publications

References 67 publications

Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (R,R)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State

Resolution of P-Sterogenic 1-Phenylphosphin-2-en-4-one 1-Oxide into Two Enantiomers by (R,R)-TADDOL and Conformational Diversity of the Phosphinenone Ring and TADDOL in the Crystal State

Synthesis of Aryldiphenylphosphine Oxides by Quaternization of Tertiary Diphenylphosphines with Aryl Bromides Followed by the Wittig Reaction

Supramolecular Diversity of Oxabicyclo[2.2.2]octenes Formed between Substituted 2H-Pyran-2-ones and Vinyl-Moiety-Containing Dienophiles

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