Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis–Arbuzov Reaction Paths

Ferao, Arturo Espinosa

doi:10.1021/acs.jpca.7b06262

Cited by 13 publications

(8 citation statements)

References 77 publications

(97 reference statements)

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“…The likely intermediacy of such a carbene was confirmed by trapping with fullerene C 60 . Three-membered oxaphosphirane rings ( F O ) were proposed , as precursors for zwitterionic species A O / A′ O ; their existence was proved by early MO calculations (HF/3-21G*) for the reaction between formaldehyde and phosphorous acid and, very recently, as intermediates in the Perkow reaction of chloroacetone with trimethylphosphite . Heavier chalcogenaphosphiranes F were also experimentally reported …”

Section: Introductionmentioning

confidence: 98%

On the Mechanism of Trimethylphosphine-Mediated Reductive Dimerization of Ketones

Ferao

2018

Inorg. Chem.

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High-level single-reference calculations reveal that trimethylphosphine-mediated reductive dimerization of properly substituted (e.g., CF) ketones proceeds via initial formation of an oxaphosphirane intermediate, with the oxygen atom occupying an equatorial position at phosphorus. In the "oxirane route", this oxaphosphirane intermediate loses a trimethylphosphine oxide unit, thus behaving as a carbene transfer agent toward a second carbonyl molecule and giving rise to a carbonyl ylide that cyclizates to the corresponding oxirane. This in turn transfers the carbene unit to a second phosphine molecule, with loss of acetone, affording a phosphorane. The latter undergoes typical Wittig reaction to the final homocoupling product through the oxaphosphetane intermediate. The alternative direct conversion of oxaphosphirane into phosphorane constitutes the lowest energy path as it skips the highest barrier oxirane → phosphorane conversion. The oxirane route is favored by the use of polar solvents and electron deficient carbonyl components. The lowest barrier most exergonic process from oxaphosphirane is the pericyclic cycloaddition of the acetone C═O bond along the endocyclic P-C bond, furnishing the stable 1,3,2-dioxaphospholane product.

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Section: Introductionmentioning

confidence: 98%

On the Mechanism of Trimethylphosphine-Mediated Reductive Dimerization of Ketones

Ferao

2018

Inorg. Chem.

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“…According to the hard/soft acid/base principle which indicates that hard acids prefer binding to hard bases while soft acids prefer binding to soft bases, the U atom of the receptors ( R ‐/ S ‐AUSRLs) corresponds to hard acid, and the coordination atom N of the guests ( cis −/ trans ‐MCHAs) corresponds to hard base, so the complexes formed by the combination of hard acid ( R ‐/ S ‐AUSRLs) with hard base ( cis −/ trans ‐MCHAs) are stable. Overall, the chemical hardness of the S ‐series complexes was larger than that of the corresponding R ‐series complexes.…”

Section: Resultsmentioning

confidence: 99%

“…The 13 C NMR chemical shifts were referenced to an internal standard (tetramethylsilane) . Before coordination, the chemical shifts of C 5 in the R ‐/ S ‐AUSRL receptors were 21.82 and 11.84 ppm, and the chemical shift values of C 6 in the guests a, b, c and d were 10.20, 18.71, 17.70 and 22.45 ppm.…”

Section: Resultsmentioning

confidence: 99%

Theoretical investigation into the coordination of R‐/S‐asymmetric uranyl–salophens containing six‐membered ring lactam with cis−/trans‐cyclohexylamines

Yang

Kong

et al. 2018

Applied Organom Chemis

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A six‐membered ring lactam derivative was introduced in a parallel manner into uranyl–salophens with R/S configuration (R‐/S‐AUSRLs), which were used as receptors to coordinate with guests of cis−/trans‐methylcyclohexylamines (cis−/trans‐MCHAs). Using density functional theory calculations at the B3LYP/6‐311G** level and RECP, an insight into the coordination complexes of the R‐/S‐AUSRLs with cis−/trans‐MCHAs was obtained. The results showed that the U atoms of receptors could coordinate with the N atoms of four kinds of cis−/trans‐1,2 or − 1,4 guests, but the two kinds of cis−/trans‐1,3 guests could not be converged by the same method in the process of structural optimization due to steric hindrance, and thus the cis−/trans‐1,3 guests could not be coordinated with the R‐/S‐AUSRLs. The mode of coordination of the R‐/S‐AUSRLs with the guests displayed a significant difference. And the change of R‐AUSRL coordination ability to the cis−/trans‐MCHAs was very large, but that of S‐AUSRL was small. Overall, the stability of the R‐series coordination complexes was higher than that of the corresponding S‐series coordination complexes, and the R‐AUSRL receptor had better coordination selectivity and higher molecular recognition to the cis−/trans‐MCHA guests than the S‐AUSRL receptor. However, the coordination ability of S‐AUSRL with the cis−/trans‐MCHAs was stronger than that of R‐AUSRL. It was expected that these results could provide insightful information and theoretical guidance for understanding the molecular recognition of R‐/S‐AUSRLs for cis−/trans‐type cyclohexylamine derivatives.

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“…Alkyl-substitution at C3 (1 b1 and 1 b2) does not lead to significant variation in RSE compared to the respective unsubstituted derivatives, and the same holds for the only σ 5 λ 5 -oxaphosphirane (1 a9) in comparison to the respective (parent) σ 3 λ 3 -derivative (1 a1). For the above mentioned pentacovalent derivative 1 a9, only the most stable isomer with the PÀ O bond in axial position as previously reported, [20,21] was computed. However, a significant increase in the ring strain can be appreciated in the case of P-alkyl (methyl) substitution when comparing both 1 g1 and 1 g3 with 1 b1 (Table 2).…”

Section: Estimation Of Rsementioning

confidence: 99%

“…[13,16] On the contrary, "high-coordinate" oxaphosphiranes received early attention, and indeed σ 5 λ 5 -oxaphosphiranes IV were proposed in 1988 as reaction intermediates, without full spectroscopic characterization, [17] and later on as a final stable product although not fully confirmed by X-ray analysis. [18] They have been also theoretically studied [19] and proposed as key intermediates in the Perkow reaction of α-haloketones with phosphites [20] and in phosphane-mediated reductive dimerization of ketones to alkenes. [21] Regarding σ 4 λ 5 -oxaphosphiranes V, they were prepared by [2 + 1] cycloaddition reactions between iminophosphanes and fluorinated ketones (E = NR), [22] or proposed to participate in ring expansion reactions (E = O).…”

Section: Introductionmentioning

confidence: 99%

Between Oxirane and Phosphirane: The Spring‐loaded Oxaphosphirane Ring

2020

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Dedicated to Professor Christoph Janiak on the occasion of his 60th birthday. Due to the potential interest of oxaphosphiranes in ringopening polymerizations, accurate ring strain energies (RSEs) of a wide variety of oxaphosphirane derivatives was computed, after validation of the optimization method by comparison with reported X-ray structures. The parent oxaphosphirane exhibits a moderate RSE (22.44 kcal/mol) that is significantly enhanced by k-P-complexation (especially with boranes), the introduction of P=O or P +-Me groups as well as exocyclic double bonds at the ring carbon, such as 3-methylene, 3-imino and 3-oxo functionalities. However, C3 alkyl substitution or pentacoordination at P in σ 5 λ 5-oxaphosphirane does not lead to significant variation of RSE. Bicyclic spiro-oxaphosphirane derivatives show an RSE decrease when the size of the spiro ring increases. A moderate linear correlation between RSE and G(r)/1(r) values calculated at the ring critical points and also with the relaxed force constant (k 0) for the PÀ C bond is observed for most oxaphosphiranes. The possibility of ring-opening polymerization by using better (anionic) nucleophiles in the initiation step can be foreseen from the exergonicity and relatively low barrier of the endocyclic CÀ O cleavage by nucleophilic attack of methanol, thus underlining the effect of the RSE as driving force compared to acyclic analogs.

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Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis–Arbuzov Reaction Paths

Cited by 13 publications

References 77 publications

On the Mechanism of Trimethylphosphine-Mediated Reductive Dimerization of Ketones

On the Mechanism of Trimethylphosphine-Mediated Reductive Dimerization of Ketones

Theoretical investigation into the coordination of R‐/S‐asymmetric uranyl–salophens containing six‐membered ring lactam with cis−/trans‐cyclohexylamines

Between Oxirane and Phosphirane: The Spring‐loaded Oxaphosphirane Ring

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