New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

Pietrusiewicz, K. Michał; Szwaczko, Katarzyna; Mirosław, Barbara; Dybała, Izabela; Jasiński, Radomir; Demchuk, Oleg M.

doi:10.3390/molecules24030571

Cited by 11 publications

(10 citation statements)

References 42 publications

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“…With the protocols for the cycloaddition and for the basic transformations of the cycloaddition product established, we turned our attention towards using these protocols for synthesis of the more rigid enantiopure P-stereogenic phosphines which could have potential relevance to asymmetric catalysis [2,4]. Towards this end, we selected cyclopentadiene, cyclohexadiene, and anthracene as well as hydroxybenzocyclobutene as dienes in order to prepare polycyclic phosphines containing rigidified bridged skeleton [65,66]. As with butadiene, also with these dienes, all the cycloadditions as well as the following transformations were tested first for conditions and efficiency using rac-1 as the substrate.…”

Section: Methodsmentioning

confidence: 99%

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

et al. 2020

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1-Phenylphosphol-2-ene 1-oxide is effectively resolved by L-menthyl bromoacetate to afford both SP and RP enantiomers of 1-phenylphosphol-2-ene 1-oxide on a multigram scale. The resolved 1-phenylphosphol-2-ene oxide has been found to undergo face-selective and endo-selective cycloadditions with a series of acyclic and cyclic dienes to produce enantiopure P-stereogenic C-P heterocycles of hexahydrophosphindole and hexahydrobenzophosphindole as well as phospha[5.2.1.02,6]decene and phospha[5.2.2.02,6]undecene structures. Conversions of these cycloadducts to the fully saturated heterocyclic systems as well as to their P (III), P = S, P = Se and P-BH3 derivatives have been demonstrated to occur with retention of configuration and preservation of configurational homogeneity at P. A perplexing case of stereomutation at P during reduction of a tricyclic β-hydroxy phosphine oxide by PhSiH3 at 80 °C has been recorded.

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Section: Methodsmentioning

confidence: 99%

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

et al. 2020

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“…A new generation M062x [55]; [56] functional, implemented in the Gaussian 09 package [57], was used. This functional has been recently used by us to solve several similar problems [58][59][60]. All stationary structures have been optimized using the advanced 6-311++G(d,p) basis set and were characterized by only positive eigenvalues in their diagonalized Hessian matrices.…”

Section: Methodsmentioning

confidence: 99%

“…For the optimized structures, thermochemical data for the temperature T = 298 K and pressure p = 1 atm were computed using vibrational analysis data. For the simulation of the solvent presence, the PCM model has been applied, similar to in previous our works [59,60].…”

Section: Methodsmentioning

confidence: 99%

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A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions

et al. 2019

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This work explores the behavior of chiral compound mixtures enriched in one of the enantiomers whilst a typical chromatography on the achiral stationary phase is employed. The influence of several factors, such as the eluent composition, ratio of the compound to the stationary phase, and the initial enatiomeric purity of the compound used on the distribution of the enantiomers in the collected chromatographic fraction, was studied. The obtained results indicate that the phenomenon of Self Disproportionation of Enantiomer (SDE) occurred in all cases, and some of the collected fractions got higher optical purities than the initial one. Thus, achiral column chromatography could be applied in some cases as the simplest approach for chiral purification. Based on the experimental results and DFT calculations, an alternative concept explaining the SDE phenomenon was proposed. Due to its generality and simplicity, SDE may also be responsible for the formation of the first chiral non-racemic compounds on the early Earth.

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“…13 04 (m, 1 H, H-9a). 13 ( 1R,4R,5R,6S,7R,9S)-Tetracyclo[5.2.2.0 1,6 .0 4,9 ]undecan-5-ol (6). A mixture of 5 (15.4 mg, 51.1 μmol, 1.0 equiv.)…”

Section: Synthetic Proceduresmentioning

confidence: 99%

The Enantiomers of Trinorbornane and Derivatives Thereof

Bizzini

Bürgi

Mayor

2020

Helvetica Chimica Acta

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Herein, we report the synthesis of the enantiomers of trinorbornane, a tetracyclic saturated hydrocarbon with the chemical formula C11H16. The preparation of these rigid carbon scaffolds was enabled by the successful chiral separation of its tricyclic precursor, thus allowing the enantiomers to be synthesized through a reductive radical cyclization reaction. Assignment of the absolute conformation of the enantiomers was achieved through VCD experiments. Further, we report an alternative cyclization procedure providing access to hydroxyl and phenyl sulfone functionalized trinorbornanes.

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New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis

Cited by 11 publications

References 42 publications

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

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

A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions

The Enantiomers of Trinorbornane and Derivatives Thereof

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