Arsenic ylides reactions

Numerous reactions of carbonyl compounds, alcohols, olefins, etc., with compounds bearing E14=X bonds in which the latter act as direct analogs of phosphorus and arsenic ylides have already been accomplished.17 Recently, an interest in reactivity of compounds with multiple E14-X bonds is increasing due to challenges of important practical applications (see,... 

Reactions of Phosphorus and Arsenic Ylides with Organocyclosilthianes and... 

As mentioned above (see Scheme 1), three main directions of the decomposition of intermediates that formed are possible when phosphorus and arsenic ylides react with compounds bearing C=X bonds 5,6,19,63,64,88 (i) elimination of R3E15=X to form olefins (Wittig type reaction) (ii) retro-Wittig type decomposition and (iii) elimination of R3E15 and formation of three-membered cycles (Corey-Chaykovsky type reaction). According to the data of Erker and coworkers,12,13,51 under kinetic control, the reaction of phosphorus ylides with thiocarbonyl compounds also affords phosphines and thiiranes, whose further transformations lead to olefins and R3PS under thermodynamic control. 

The thermodynamic data presented in Table XYI are calculated for the temperature T=0K. Note that the entropy factor favors betaine decomposition via directions A and B at higher temperatures. The reactions of organoelement analogs of carbenes with phosphorus and arsenic ylides are yet poorly studied. The presented above results of calculations allow an optimistic prognosis about the possibility of developing a new method for the synthesis of elementaolefins R2E14=CH2 (E14 = Si, Ge, Sn) on the basis of these reactions. 

For example, see Johnson LaCount Tetrahedron 1960, 9, 130 Bestmann Kratzer Chem. Ber. 1962, 95, 1894. An arsenic ylide has been used in a catalytic version of the Wittig reaction that is. the R AsO product is constantly regenerated to produce more arsenic ylide Shi Wang Wang Huang J. Org. Chem. 1989, 54, 2027. 

Reactions of Phosphonic and Arsenic Ylides with Electron Deficient Alkynes and Synthesis of Polyfunctional Fluoroorganics ... 

Very little is known about chemical reactions of arsenic ylides, and the examples reported in the literature have been conducted with arylated species often bearing stabilizing substituents (11, 26). Even from these examples it appears that often the course of the reaction is entirely different from analogous processes with phosphorus ylides (50). 

It has been pointed out previously that silylation of ylides leads to stabilized products and that this is only one example of the very general phenomenon of carbanion stabilization through silicon (34, 61, 72). This effect was also found for arsenic ylides (34, 73), and is the basis for the preparation of other compounds of this series. The influence of silicon is by no means solely an electronic effect. In many cases, where alkylsilyl substituents are introduced, a steric effect may well dominate, which may reduce lattice energies for salts in transylidation reactions, preventing intermolecular contacts in decomposition processes, and rendering the formation of salt adducts unfavorable. This steric effect is reduced to a minimum, but not eliminated, if simple SiH3 groups are employed (61). Even then, however, a pronounced silicon effect is found, which must be based on electronic influences (49, 60, 61). 

Reaction of arsenic ylides 42 with methanol or with ethylene oxide gives aIkoxy(tetra-methyl)arsoranes as shown in equations 349 and 350 . ... 

Another arsonium ylide reaction involves a notable transylidation reaction between a phosphorus and an arsenic ylide (Scheme 6). A useful arsenic ylide which provides a hydroxymethyl epoxide has been reported (equation IS) note the use of biphasic reaction conditions for ylide generation. 

The arsenic ylide PhaAs CHj has now been isolated as an unstable solid from a reaction between PhaAsMeBr and sodium amide in THF, and the analogous methyl ylide Me3As==CH2 is the immediate precursor of an unusual five-coordinate tetra-alkylarsonium compound. Methanol adds to the ylide to give Mc4AsOMe, which from low-temperature n.m.r. spectra has the structure (120). 

Aldehydes.- The reactions of phosphorus ylides, PO-activated carbanions and iminophosphoranes have been incorporated into CAMEO, an interactive computer program for the mechanistic evaluation of organic reactions.8 The chemistry and synthetic applications of phosphorus and arsenic ylides and PO-stabilised carbanions have been reviewed. ... 

With HMPA, Wittig reactions that give ( )-alkenes were also observed (eq 18), as was the directed selectivity of a semista-bilized arsonium ylide towards carbonyl compounds. The arsenic ylide was generated from LDA in THF or THF/HMPA solution to give exclusively epoxide (eq 19) or diene (eq 20), respectively. ... 

The formation of the heterocycle 1 from the xylylene-bis-phosphonium salt 2 and PCI3 proceeds via a detectable intermediate 3 in a cascade of condensation reactions that is terminated by spontaneous heterolysis of the last remaining P-Cl bond in a cyclic bis-ylide-substituted chlorophosphine formed (Scheme 1) [15]. The reaction scheme is applicable to an arsenic analogue of 1 [15] and to bis-phosphonio-benzophospholides with different triaryl-, aryl-alkyl- and aryl-vinyl-phosphonio groups [16, 18, 19], but failed for trialkylphosphonio-substituted cations here, insufficient acidity prohibited obviously quantitative deprotonation of the phosphonium salts, and only mixtures of products with unreacted starting materials were obtained [19]. The cations were isolated as chloride or bromide salts, but conversion of the anions by complexation with Lewis-acids or metathesis was easily feasible [16, 18, 19] and even salts with organometallic anions ([Co(CO)4] , [CpM(CO)3] (M=Mo, W) were accessible [20]. 

Since this discovery a number of binuclear complexes of this type have been isolated, including the arsenic analog of the above (57) and compounds prepared from more exotic ylide precursors (58-60). A polymeric gold(I) complex was obtained by reaction of [AuCl(PMe3)] with the biden-tate ylide CH2=PMe2(CH2)6PMe2=CH2 (60). 

In 1953 Wittig and Geissler (100) reported that methylene triphenyl-phosphorane reacted with benzophenone to form 1,1-diphenylethene and triphenylphosphine oxide. This experiment marked the birth of the Wittig reaction, a novel method for the conversion of carbonyl groups to olefins, and the entry of ylides into the arsenal of important synthetic tools. Since... 

However, certain phosphonium ylides, such as those with an electron-withdrawing substituent in the alkylidene moiety, are relatively unreac-tive toward certain substrates such as ketones (22, 77, 95). This led us to consider whether arsonium ylides might be preferable to phosphonium ylides in certain reactions (48, 94). The overlap of the p orbitals of carbon with d orbitals of arsenic is less effective than with d orbitals of phosphorus. Therefore the covalent canonical form (la) should make a smaller contribution to the overall structure of arsonium ylides than to that of the corresponding phosphonium ylides. 

The nature of the arsonium substituents also influences the course of the reaction. Gosney et al. (33) studied the reaction between arsonium salts of type 50 and benzaldehyde in THF using -butyllithium to generate the ylide. The results, summarized in Table IX, clearly show that electron-donating substituents at the arsenic atom promote the formation of al-kenes. At one extreme, the reaction of 0) gives a notable yield of stilbene almost to the exclusion of stilbene oxide, whereas at the other, the reaction of (a) yields predominantly stilbene oxide. Table IX shows that electron-donating substituents at arsenic increase the ratio of alkene to epoxide. 

Ylides of other elements have been used much less commonly than sulfur ylides in cyclopropanations. Rather, other ylides are better known for their uses in other types of reactions, the best example being the use of phosphonium ylides in the Wittig reaction with carbonyl compounds to give alkenes. Nonetheless, some cases of cyclopropanations have been reported with phosphonium ylides and the related arsenic derivatives. Examples are given in Table 9. 

When this method is applied to compounds of phosphorus and arsenic, the components undergo an entirely different reaction, and alkylidene trialkyl derivatives of these elements (ylides) are obtained 102, 104). Thus, instead of the introduction of an additional alkyl substituent at the central element, as observed with antimony, a deprotonation at one of the a-carbon atoms adjacent to phosphorus and arsenic occurs ... 

In this chapter, we will review the use of ylides as enantioselective organocata-lysts. Three main types of asymmetric reaction have been achieved using ylides as catalysts, namely epoxidation, aziridination, and cyclopropanation. Each of these will be dealt with in turn. The use of an ylide to achieve these transformations involves the construction of a C-C bond, a three-membered ring, and two new adjacent stereocenters with control of absolute and relative stereochemistry in one step. These are potentially very efficient transformations in the synthetic chemist s arsenal, but they are also challenging ones to control, as we shall see. Sulfur ylides dominate in these types of transformations because they show the best combination of ylide stability [1] with leaving group ability [2] of the onium ion in the intermediate betaine. In addition, the use of nitrogen, selenium and tellurium ylides as catalysts will also be described. 

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