Chemistry of pentacoordinated anti-apicophilic phosphorus compounds

Kobayashi, Junji; Kawashima, Takayuki

doi:10.1016/j.crci.2010.06.010

Cited by 18 publications

(12 citation statements)

References 38 publications

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“…(4) If the aryl group is polyaromatic without substituents and heteroatoms, the alkaline hydrolysis of the corresponding aryltriphenylphosphonium salts favors the departure of this aryl group, leading to the formation of Ph 3 PO and arenes ( 2i and 2w ); if the polyaromatic aryl bears an electron-donating group, aryldiphenylphosphine oxides 2 could also be obtained in high yields ( 2u and 2v ). These observations are generally in agreement with the apicofilicity rule , that electronegative and small substituents prefer apical positions in the trigonal bipyramidal structure of pentacoordinate phosphorus compounds.…”

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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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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“…5(3) in the basal plane and 85.0(3) -92.9(2) between basal and apical positions. 1,12,17 Phosphazenes 14a,b monosubstituted at carbon  to the phosphorus provided the spirophosphoranes 17e,f in the reaction with 2,2-dimethyloxirane, respectively, in high NMR yields (92-93%) and with improved diastereoselectivity in favour of the cis isomer, in which [1,2] steric interactions with the rigid benzoazaphospholone moiety and the substituent at carbon C3 are minimized. Compounds 17e,f undergo easily hydrolysis and they were characterized from the crude reaction mixture without further purification.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…1,12,17 Spiro[4,4]phosphoranes 3 bearing two ML units have been extensively investigated in terms of fluxionality 17b and reactivity. The synthetic applications of compounds 3 are based on reactions at the phosphorus center with nucleophiles 18 and electrophiles (after P-H deprotonation) 19 including epoxides, 20 and at the carbon 12,17,21 or nitrogen atom 22 adjacent to the phosphorus after proton abstraction with a strong base (Figure 1). Interestingly, the protic solvent mediated or acid catalyzed hydrolysis of spiro [4,4] We have reported that (N-methoxycarbonyl)phosphazenes 4 are useful reagents for the stereoselective synthesis of di-triand tetra-substituted alkenes 5 via C  monolithiation (Scheme 1, route a) 24 or C  ,Cortho dianions 7 (route b).…”

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confidence: 99%

Synthesis of Pentacoordinated Spiro[4.4]phosphoranes by Reaction of Cyclic Phosphazenyl Anions with Epoxides: Study of their P-Remote Functionalization and Hydrolysis

López¹,

Ortiz²,

Peraza³

et al. 2021

Synthesis

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The synthesis of a new family of pentacoordinated spiro[4,4]phosphoranes stabilized by the ortho-benzamide bidentate ligand (oBA,-C6H4-2-C(O)NH-) through reaction of Cα -Cortho-dilithiated phosphazenes with oxiranes is reported. Mixtures of epimers that differ in configuration at the phosphorus atom were obtained with moderate to high yields and diastereoselectivities. C3-disubstituted derivatives could be separated, which provided access to enantiopure products arising from the reaction with (R)-2-phenyloxirane. Stereomutation was observed by heating the spirophosphoranes at 100 ºC. Directed ortho lithiation of spirophoshoranes followed by electrophilic quench reactions including carbon-based and heteroatom-based electrophiles afforded derivatives functionalized in remote position with respect to the phosphorus atom. Benzoic acid catalyzed hydrolysis of spirophosphoranes furnished ortho-(hydroxyalkylphosphoryl)benzamides by cleavage of the P‒O and P‒N bonds with retention of the phosphorus configuration. In contrast, alkaline hydrolysis led to the formation of γ-hydroxyphosphinic acids and benzamide.

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“…One of the most interesting and intriguing classes of organophosphorus compounds are the 1,2-oxaphosphetanes—four-membered heterocycles containing pentacoordinated phosphorus [1,2,3,4,5,6,7]. Since 1,2-oxaphosphetanes are well-known intermediates in the Wittig reaction, a number of efforts have been made for their structural characterization both in solution and the solid state [8,9,10,11,12,13].…”

Section: Introductionmentioning

confidence: 99%

“…Among the stable oxaphosphetanes [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22], 2-halo-1,2λ 5 -oxaphosphetanes 14 , which possess relatively high stability and diverse reactivity, attract particular interest [23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38] (Scheme 7). These oxaphosphetanes containing fluorine, chlorine or bromine atoms bonded to phosphorus are an interesting class of pentacoordinated phosphorus heterocycles possessing peculiar properties.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

Kolodiazhna

Kolodiazhnyi

2016

Molecules

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Abstract:Results of research into four-membered 2-halo-1,2λ 5 -oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ 5 -oxaphosphetanes by reaction of P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-cycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ 5 -oxaphosphetanes were isolated as individual compounds and their structures were confirmed by 1 H-, 13 C-, 19 F-and 31 P-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halo-1,2λ 5 -oxaphosphetanes are reviewed. The 2-chloro-1,2λ 5 -oxaphosphetanes, rearrange with formation of 2-chloroalkyl-phosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ 5 -oxaphosphetanes are analyzed. The 2-halo-1,2λ 5 -oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl-or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.

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Chemistry of pentacoordinated anti-apicophilic phosphorus compounds

Cited by 18 publications

References 38 publications

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

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

Synthesis of Pentacoordinated Spiro[4.4]phosphoranes by Reaction of Cyclic Phosphazenyl Anions with Epoxides: Study of their P-Remote Functionalization and Hydrolysis

Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ5-oxaphosphetanes

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