Acylphosphonate

Takamizawa et al. developed a general ring-expansion reaction of heterocycles that, applied to thiazolium salts, yields 1,4-thiazines (496, 497) thiamine (220) reacts with dialkyl acylphosphonates (221) to give the tricyclic 1,4-thiazine (222) (498), which is easily hydrolyzed to dihydro-1,4-thiazinone (223) (499) (Scheme 106). In the case of thiazolium slats containing no functional groups (224), 1,4-thiazine derivatives (226) were directly obtained in fairly good yields (Scheme 107). 

Dialkyl phosphites react with acyl halides such as lauroyl chloride to yield surface-active acid esters of acylphosphonic acid [84-87] see Eq. (40). 

A useful approach for the preparation of chiral (3-aminophospho-nic acids from the naturally occurring a-amino acids has been reported.139 The overall scheme (Equation 3.4) involves formation of the phthalimide-acid halide from the starting a-amino acid followed by a Michaelis-Arbuzov reaction with triethyl phosphite to give the acylphosphonate. Complete reduction of the carbonyl group in three steps followed by hydrolysis of the ester and amide linkages provides the target material in very high yield without racemization (>99% ee). 

Sekine, M., Kume, A., Nakajima, M., and Hata, T., A new method for acylation of enolates by means of dialkyl acylphosphonates as acylating agents, Chem. Lett., 1087, 1981. 

Evans et al. (219, 220) examined the use of electron-poor heterodienes as partners in cycloadditions with electron-rich alkenes under copper catalysis. In particular, a,p-unsaturated acylphosphonates and keto-esters afford hetero-Diels-Alder adducts in high selectivities when treated with enol ethers in the presence of catalysts 269c and 269d. 

Various substituted unsaturated acylphosphonates participate in highly dias-tereoselective and enantioselective cycloadditions with vinyl ethers, Eqs. 177 and 178. It is intriguing to note that catalysts [(.V,.Y)-f-Bu-box]Cu (OTf)2 (269c) and [(.V,.S )-Ph-box]Cu (OTf>2 (269d) possessing the same sense of chirality afford opposite antipodes of the cycloadduct in comparable selectivities. Cyclopentadiene was found to react with acylphosphonates to give a mixture of the normal Diels-Alder adduct and the inverse electron demand hetero-Diels-Alder adduct (35 65), Eq. 179. This result may be contrasted with crotonylimide, which furnishes the normal demand Diels-Alder adduct exclusively. 

Figure 26. Proposed stereochemical model for the hetero-Diels-Alder reaction of ethyl vinyl ether and acylphosphonate catalyzed by 55c-Cu(II) complex.

The hetero-Diels-Alder reaction between a,p-unsaturatcd ketoesters and nucleophilic alkenes has been described in two concurrent and independent reports (220, 222). As with acylphosphonates, these proved to be excellent substrates for catalyst 269c. The reaction proceeds efficiently in THF at low temperatures providing the cycloadduct in >99% ee at -78°C. Indeed, the impressive selectivity exhibited under these conditions allows the reaction to be conducted at a convenient temperature of 0°C, using the hydrated catalyst 266c in the presence of molecular sieves, Eq. 181. Observed diastereoselectivities... 

The condensation of aldehydes and ketones with aminoacetonitriles, although it requires more vigorous soliddiquid catalytic conditions to produce the cyano-enamines, is preferable in many respects to the traditional Wittig-Horner or Peterson procedures [45]. Hydroxyalkylphosphonates are obtained from the catalysed aldol condensation of nitromethane with acylphosphonates [46]. 

Acyclic cationic systems, chalcogen-halogen compounds, 35 299-301 Acylarsonic acids, 44 217 Acyldiazenido complexes, mechanisms of formation, 27 223-225 Acylium cation, 9 231, 241-243 Acylphosphonic acids, 44 217 Acylsilane, hydrolysis, 42 173 Adamantane... 

Reaction of Azolium Ylides with Dialkyl Acylphosphonate New Synthesis of Heterocyclic Compounds A. Takamizawa et al., Heterocycles, 1974, 2, 521-554. 

Acylphosphonates, e.g. (5), possess highly reactive carbonyl groups and—somewhat like trilialomethyl ketones—exhibit both ketone and carboxy character, forming oximes and adducts, and also carboxylate derivatives via C—P bond cleavage.7 Their hemiacetal derivatives have been studied by 31P-NMR in the presence of alcohols, for the representative acetyl and benzoyl compounds (5 R = Me, Ph). Equilibrium and... 

Acylphosphonates generate acyl anion equivalents with cyanide via phosphonate-phosphate rearrangement. These anions react with aldehydes to provide cross-benzoin... 

The oxazoliumcarboxylic acid (147) is easily decarboxylated via the ylide (148) the neutral compound (149) is much more stable due to the low equilibrium concentration of the zwitterionic tautomer (150 Scheme 7). Oxazolium salts lacking substituents at the 2-position react with dialkyl acylphosphonates in the presence of triethylamine to give mixtures of l,4-oxazin-3-ones and 2-azetidinones the reaction (see Scheme 8) proceeds by electrophilic attack of the phosphonate on an oxazolium ylide, e.g. (151), followed by insertion of oxygen into the carbon-phosphorus bond, ring-opening, and formation of the enolate anion (152) which can cyclize in two alternative ways with expulsion of the phosphonate group. 

The reaction is also facile (no external heating) and proceeds in high yield when the snbstrate is an acyl halide or related material. Snch reactions, producing acylphosphonate derivatives (eqnation 28), are of nse for the preparation of componnds for a variety of practical applications. ... 

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