Ylide compounds electrocyclizations

Cyclization of a thiocarbonyl ylide with the C=C-bond of an aromatic ring was observed in the reaction of aryl biphenyl-2-yl ketones with di(tosyl)diazomethane in the presence of Rh2(OAc)4 (189). In the case where the aryl ring contains a 4-methoxy group, benzo[c]thiophene (164) was the only product formed. In contrast, when the aryl ring consists of a 2,4,6-trimethylphenyl group, compounds 165 and 166 were produced. It would seem that after 1,5-dipolar electrocyclization of the intermediate thiocarbonyl ylide occurs, aromatization then takes place by elimination of toluenesulfinic acid or methyl toluenesulfinate. 

Fluoro-substituted dihydrofuro[3,2-r ]pyridinones are obtained from the thermolysis reaction of cyclopropa[3]-furo[2,3-f]pyrroles, 134, along with the loss of HF (Equation 67) <2005SL1006>. Compound 134 is generated from pyrroles via reaction with a carbene to give an azomethine ylide which undergoes an electrocyclization reaction. 

Thiocarbonyl ylides are both nucleophilic and basic compounds (40,41,86). For example, adamantanethione (5)-methylide (52) is able to deprotonate its precursor, the corresponding 2,5-dihydro-1,3,4-thiadiazole, and a 1 1 adduct is formed in a multistep reaction (40,86). Thioxonium ion (56) (Scheme 5.22) was proposed as a reactive intermediate. On the other hand, thiofenchone (S)-methylide (48) is not able to deprotonate its precursor but instead undergoes electrocyclization to give a mixture of diastereoisomeric thiiranes (41,87,88). The addition of a trace of acetic acid changes the reaction course remarkably, and instead of an electrocyclization product, the new isomer 51 was isolated (41,87) (Scheme 5.18). The formation of 51 is the result of a Wagner-Meerwein rearrangement of thioxonium ion 49. 

As mentioned on pages 317 and 324, the 1,3-dipolar electrocyclization of thiocarbonyl ylides leads to thiirane derivatives, which represents an excellent method for the preparation of those three-membered rings. Typically, thiiranes are isolated as the final products, but in some instances they are produced as intermediate compounds which spontaneously desulfurize to give alkenes [twofold extrusion (47,48)]. 

The reaction of a thiocarbonyl and a-oxodiazo compound that leads to 1,3-oxathioles has been rationalized by a 1,5-dipolar electrocyclization reaction (178). It was suggested that an intermediate thiocarbonyl ylide bearing a C=0 function at the a-position (extended dipole) was first formed. Due to the low reactivity of a-oxodiazo compounds, these reactions were carried out at elevated temperatures or in the presence of rhodium acetate as the catalyst. In some cases, catalysis by LiC104 was also reported (77-80). 

The metal-catalyzed formation of 2,3-dihydrothiophene derivatives via a 1,5-dipolar electrocyclization has been reported by Hamaguchi et al. (124). For example, the Rh2(OAc)4-catalyzed reaction of vinyldiazo compound 159 (R = Ph) with xanthione (160) produced the spirocyclic dihydrothiophene 161. In contrast, when 159 containing a methyl group (R = Me) was used, thiirane 162 was the sole product (Scheme 5.48). This result was rationalized by the selective formation of an intermediate thiocarbonyl ylide 163 with (Z)- and (E)-configuration, respectively. 

The 877-electrocyclization of carbonyl ylides of type B, e.g., the ylide derived from oxirane 145, was less favored than the 6n electrocyclization to yield a mixture of three compounds 146 and isomers 147 (in a ratio of 3 7). The annulated vinylfuran derivative 147 formed as mixture of isomers (cis-trans 4 3) while the stereochemistry of the single isomer of 146 has been established by X-ray analysis of the Diels-Alder adduct (Scheme 44) [81TLC194953 85CB4035]. 

The generation and reactivity of conjugated azomethine ylides has been reviewed.148 1,3-Dipolar cycloaddition and 1,5- and 1,7-electrocyclizations have been described as powerful strategies for the synthesis of monocyclic and annulated five- and seven-membered nitrogen heterocyclic compounds. 

Woerpel and Calad tested for the formation of the silacarbonyl ylide by interrogating the behavior of the electrophilic silver silylenoid intermediate 115 toward a,(3-unsaturated carbonyl compounds (Scheme 7.37).82 They hypothesized that formation of silacarbonyl ylide 131 might trigger a 6jt-electrocyclization to form oxasilacyclopentene 132. As anticipated, exposure of cyclohexene silacyclopropane 58 to substoichiometric amounts of silver trifluoroacetate in the presence of a,(3-unsaturated carbonyl compounds 130 produced oxasilacyclopentenes 132. The reaction tolerated a substitution at the a and/or (3 position and was general for both esters and ketones. 

Another class of three-membered heterocyclic compounds that exhibit photochromic activity via 1,3-electrocyclization reaction is the aziridines. For the most part, similar to the oxiranes, these materials require low temperatures to demonstrate photochromic behavior [6]. Also, some of the photochromic transformations are not completely reversible. However, several room temperature stable ylides have been reported for aziridines possessing the general form of Scheme 5 [I], where X and Y may be a mixed combination of nitro, methoxy, and hydrogen groups. The... 

Quinazoline-4(3// )-thione condenses with ethyl bromocyanoacetate " and ethyl 2-chloro-3-oxobutanoate in the presence of sodium ethoxide in ethanol with sulfur extrusion to form ethyl 2-cyano-2-(quinazolin-4-ylidene)acetate (5, R = CN) and ethyl 2-(quinazolin-4-ylidene)-acetate (5, R = H), respectively. It has been suggested that the initial adduct of quinazoline-4(3//)-thione and a methylene compound is deprotonated to give the corresponding ylide which undergoes electrocyclic closure to a thiirane derivative and then desulfurization. A C - C double bond is formed between the methylene carbon atom and the electrophilic carbon C4, providing an alternative to the Wittig reaction. 

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