Ylides properties

Imidazolines (and isomers) can act as dienophiles in Diels-Alder reactions (see CHEC-I). The ylide properties of l,3,4,5-tetramethyl-2-methylene-4-iinidazoline (136) are demonstrated by the reactions of Scheme 67. This compound has the 7t-electrons delocalized over the whole ring and the exocyclic double bond which shows characteristic shortening <93CC1136). 

To understand the mechanism of the Wittig reaction, we need to exanine the structure and properties of ylides. Ylides are neutral molecules that have two oppositely... 

Similar results were obtained when 4,4 -bipyridyl was quaternized with p-bis(bromo-acetyl) benzene in refluxing benzene to give a 92% yield of the blue-green salt. Potassium carbonate treatment of their blue-green salt gave a greenish black polymeric ylide (Scheme 11), which was similar in appearance and properties to (Scheme 12). 

A novel chiral dissymmetric chelating Hgand, the non-stabiUzed phosphonium ylide of (R)-BINAP 44, allowed in presence of [Rh(cod)Cl]2 the synthesis of a new type of eight-membered metallacycle, the stable rhodium(I) complex 45, interesting for its potential catalytic properties (Scheme 19) [81]. In contrast to the reactions of stabihzed ylides with cyclooctadienyl palladium or platinum complexes (see Scheme 20), the cyclooctadiene is not attacked by the carbanionic center. Notice that the reactions of ester-stabilized phosphonium ylides of BINAP with rhodium(I) (and also with palladium(II)) complexes lead to the formation of the corresponding chelated compounds but this time with an equilibrium be-... 

Trzcinskabancroft, B., Knachel, H., Dudis, D., Delord, T.J. and Marler, D.O. (1985) Experimental And Theoretical-Studies Of Dinudear Gold(I) And Gold(II) Phosphorus Ylide Complexes - Oxidative Addition, Halide Exchange, And Structural-Properties Including The Crystal And Molecular-Structures Of [Au (CH2)2PPh2]2 And [Au(CH2)2PPh2]2(CH3) Bri. Journal of the American Chemical Society, 107(24), 6908-6915. 

In contrast to ethyl diazoacetate, diethyl diazomalonate reacts with allyl bromide in the presence of Rh2(OAc)4 to give the ylide-derived diester favored by far over the cyclopropane (at 60 °C 93 7 ratio). This finding bespeaks the greater electrophilic selectivity of the carbenoid derived from ethyl diazomalonate. For reasons unknown, this property is not expressed, however, in the reaction with allyl chloride, as the carbenoids from both ethyl diazoacetate and diethyl diazomalonate exhibit a similarly high preference for cyclopropanation. 

Chiral sulfonium ylides have been known for some 30 years, and their stereochemistry and properties have been studied.15 Optically active selenonium ylides were obtained by reacting selenoxides with 1,3-cyclohexanedione under asymmetric conditions by Sakaki and Oae in 1976 for the first time,16 and also optically resolved by fractional recrystallization of the diastereomeric mixtures in the early 1990s.17 In 1995, optically active selenonium ylides 6 were obtained in over 99% de by nucleophilic substitution of optically active chloroselenurane or selenoxide with active methylene compounds with retention of configuration.18 The absolute configurations were determined by X-ray analysis of one... 

The first kinetically stable dibenzosilafulvene (7), whose structure and properties should more correctly be described by the resonance hybrid 7a 7b with a great contribution of the ylide form 7a, reacts with phosphorus ylide to form betaine (8), which is rearranged, under thermodynamically controlled conditions, into the salt (9) (Scheme 4).24,25... 

Bismuthonium ylides, 4 34 Bismuth(III) oxide, 4 23-24 Bismuth oxide(l l), 4 23 Bismuth oxide(l 2), 4 23 Bismuth oxide(2 4), 4 23 Bismuth oxide(3 5), 4 23 Bismuth oxide(4 9), 4 23 Bismuth oxide halides, 4 23 Bismuth oxides, 4 23-24 Bismuth oxybromide, 4 23 Bismuth oxychloride, 4 23 physical properties of, 4 20t pigment used in makeups, 7 836t Bismuth oxyfluoride, 4 23 Bismuth oxyiodide, 4 23 Bismuth pentafluoride, 4 22 physical properties of, 4 20t Bismuth phosphate, 4 25... 

Diaminocarbene complexes were reported as early as 1968 [152], Preparation and applications of such complexes have been reviewed [153], Because of 7t-electron donation by both nitrogen atoms, diaminocarbenes are very weak tt-acceptors and have binding properties towards low-valent transition metals similar to those of phosphines or pyridines [18,153]. For this reason diaminocarbenes form complexes with a broad range of different metals, including those of the titanium group. Titanium does not usually form stable donor-substituted carbene complexes, but rather ylide-like, nucleophilic carbene complexes with non-heteroatom-substituted carbenes (Chapter 3). 

The k C bonding mode includes most of the reported work on ylides. However, modifications of the structure of the yhde could be advantageous, in particular the introduction of additional donor atoms to form chelate hgands. The combination of the pure a-donor properties of the ylide with those of the auxiliary donor atom could be used for tuning the steric and electronic properties of yhde complexes. There are reports of useful C,P- and C,C-chelates, which will be detailed here. 

Recent research on aminocarbenes has led to the development of a very fruitful field. The synthesis of relevant complexes (Scheme 19) such as aminobis(yhde) carbene species (69) [147], cyclic C-amino P-ylides (70) (easily transformed into carbenes) [148] and their corresponding complexes (71) [149], and special ylides (72), which also transform very easily into carbenes by loss of pyridinium group, has been reported. Emphasis has been made on the transformation between ylides and carbenes and on the donor properties of the ylides. From the results obtained the ylides have shown a stronger a-donor behavior compared with the carbenes. 

Attaching a Ceo cluster to an [Ru(bpy)3] + core has been achieved by 1,3-dipolar cycloaddition of azomethine ylides to the fullerene. The electrochemistry of the complex is complicated a one-electron reversible oxidation of the Ru center, five one-electron reversible reductions associated with the Ceo cage, and five more reversible reductions centered on the bpy ligands. The photophysical properties of the complex have been discussed. ... 

The ylides and imides are present as monomers, and the bismuth center adopts a distorted tetrahedral geometry. In contrast, the structural properties of the bismuth oxides vary widely depending on the aryl ligands attached to the bismuth center the oxides exist as hydrates, dimers, or polymers in solution and in the solid state. X-ray structural analysis of an oxide dimer revealed that the bismuth center has a distorted, trigonal bipyramidal geometry with the two oxygen atoms at the apical and equatorial positions [47, 48]. 

Isomunchnones play a large part in the synthetic efforts Padwa and co-workers (91-94,96,98,110,111). The Lycopodium alkaloids are a large family of natural products and have inspired numerous synthetic routes to approach these compounds. Interest in this class of alkaloids stems from the myriad of biological properties they exhibit. Padwa utilized the carbonyl ylide methodology in tandem with a cationic 71-cyclization to complete a formal synthesis of ( ) lycopodine (Scheme 4.55) (96,112). 

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