Synthese von β‐Nitroalkenyl‐benzylphosphorylderivaten

Czekanski, T.; Witek, S.; Costisella, Burkhard; Groß, H.

doi:10.1002/prac.19813230302

Cited by 6 publications

(4 citation statements)

References 6 publications

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“…Bis(diethoxyphosphoryl)methane was prepared from triethyl phosphite and CH 2 Br 2 according to the literature procedure. 18 Dimethyl trimethylsilyl phosphite was prepared according to the literature procedure. 19 The…”

Section: Methodsmentioning

confidence: 99%

Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

Kadyrov¹,

Selke²,

Giernoth³

et al. 1999

Synthesis

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E)-3-Dialkoxyphosphorylbut-2-enoates, readily available by the dehydration of the 3-dialkoxyphosphoryl-3-hydroxybutyrates are converted to 3-dialkoxyphosphorylbut-3-enoates by Pd(II)-catalyzed photochemically assisted double bond migration. Hydrogenation of the latter catalyzed by chiral rhodium complexes affords 3-dialkoxyphosphorylbutyrates with higher rates and enantioselectivity (98% ee) than the hydrogenation of the (E)-3-dialkoxyphosphorylbut-2-enoates. The low activity of the rhodium complexes with bisphosphinite ligands is caused by low affinity for complexation of the unsaturated phosphonate.Phosphonic acids are of respectable importance due to their wide biochemical activities 1 and especially chiral derivatives have attracted particular attention. 1b-f Our interest in the synthesis of previously unknown 3-(dialkoxyphosphoryl)but-3-enoates of the type 8 arose during the investigations of the rhodium dihydrido substrate complexes in enantioselectively catalyzed hydrogenation of dimethyl itaconate. 2 At that time we were unable to make an unambiguous assignment of the NMR signals due to spatial encroachment of substrate in the coordination sphere of the complex. We hoped to get unequivocal results with a substrate analogous to dimethyl itaconate but carrying phosphorus as a marker atom to give indicative couplings in the NMR spectra. We have now found a valuable route for the preparation of new (dialkoxyphosphoryl)butenoates which we report here together with some results on their highly enantioselective hydrogenation.There are several methods reported in the literature for the synthesis of vinylphosphonates. The hydrophosphonylation of alkynes is one of the most versatile synthetic approaches to alkenylphosphonates but, mostly, gives a mixture of products. 1b,3 Another method includes palladium-catalyzed coupling of various vinyl bromides with dialkyl phosphites. 4 The availability of the starting vinyl bromides is the limiting step of this synthetic strategy. An elegant synthesis of 1-methylenealkanephosphonates consists of Wittig reaction of acylphosphonates with methylenetriphenylphosphorane. 5 The starting methyl 3-oxo-3-(dimethoxyphosphoryl)propionate (1) is easily obtained by Arbuzov reaction of trimethyl phosphite with methyl malonyl chloride. 6 However, due to the full enolization of this ketophosphonate 1 (determined by NMR) it protonates the methylenephosphorane according to Scheme 1 to give quantitatively [(E)-1-dimethoxyphosphoryl-2-methoxycarbonylvinyloxy]methyltriphenylphosphorane (2). Scheme 1In another approach, methyl 3-bis(diethoxyphosphoryl)propionate (3) is prepared by metallation of bis(diethoxyphosphoryl)methane with NaH and subsequent treatment with methyl chloroacetate. The HornerWadsworth-Emmons condensation with formaldehyde under a variety of conditions (MeONa/MeOH, t-BuOK/tBuOH, NaH/THF, MgBr 2 /Et 2 O/THF) leads to complex mixtures of products from which the starting material and the phosphonoolefin 7 are isolated. Evidently, the initially formed vinylphosphonate 8 undergoes ...

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Section: Methodsmentioning

confidence: 99%

Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

Kadyrov¹,

Selke²,

Giernoth³

et al. 1999

Synthesis

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“…37 Altering the various reaction conditions does not improve the yield. 81,82 The choice of starting phosphite plays an important role, e.g. triisopropyl phosphite gives a better yield (48 %) given the inert nature of isopropylbromide, generated in the reaction, toward trisopropyl phosphite.…”

Section: Michaelis-arbuzov Reactionmentioning

confidence: 99%

“…Michaelis-Becker reaction : The UV light-induced Michaelis-Becker reaction between diethyl sodiophosphite and dibromomethane in hexane with (t-BuO) 2 as initiator gives the diethyl bromomethylphosphonate which was converted, without isolation, into tetraethyl methylenebisphosphonate (55-87 % yield). 82 Kinnear-Perren reaction : In the presence of AlBr 3 , the reaction between dibromomethane and phosphorus tribromide gives bromomethylphosphonyl dibromide in 60 % yield. 61 Further treatment of this acid bromide with a sodium alkoxide in alcohol yields the corresponding dialkyl bromomethylphosphonate (ethanol, 49 % ; allyl alcohol, 43 % overall yield).…”

Section: Michaelis-arbuzov Reactionmentioning

confidence: 99%

The Synthesis of Dialkyl α-Halogenated Methylphosphonates

Waschbüsch¹,

Carran²,

Marinetti³

et al. 1997

Synthesis

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“…As a result of the exceptionally interesting biological properties of bisphosphates, numerous books and reviews have been published that summarize biomedical 5,[42][43][44][45][46][47][48][49] and synthetic aspects 47,[50][51][52][53][54][55][56] of the chemistry of bisphosphonates. However, the chemistry AMBPs has never been reviewed systematically.…”

Section: Introduction and Short Overview Of Biomedical Applicationsmentioning

confidence: 99%

1-Amino-1,1-bisphosphonates. Fundamental syntheses and new developments

Romanenko¹,

Kukhar²

2012

Arkivoc

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1-Amino-1,1-bisphosphonates have become increasingly important in different fields of chemistry, medicine and agriculture. The combination of the unique physical, chemical and biological properties of methylenebisphosphonate and aminophosphonate fragments opens wide possibilities for the design of biologically active compounds including therapeutic agents to treat bone disorders related to calcium metabolism, immunomodulators, anti-infectives and plant growth regulators. The scope of this review is to summarize the existing strategies for the preparation of diversely functionalized 1-amino-1,1-bisphosphonates and to illustrate their utility as synthetic building blocks.

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Synthese von β‐Nitroalkenyl‐benzylphosphorylderivaten

Cited by 6 publications

References 6 publications

Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

Synthesis of New 3-(Dialkoxyphosphoryl)butenoates and Their Enantioselective Hydrogenation

The Synthesis of Dialkyl α-Halogenated Methylphosphonates

1-Amino-1,1-bisphosphonates. Fundamental syntheses and new developments

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