Of pyrans

These reactions are related to the formation of pyrroles and quinolines from aminocarbonyl compounds and acetylenes (582,583) and may be contrasted with the formation of pyran derivatives by electrophilic attack on an enamine, followed by addition of an oxygen function to the imonium carbon (584-590). 

Despite the increasing information on the photochemistry of 2,4-dienones and other unsaturated ketones, as well as on the ring-chain valence isomerism of halogen-substituted pyran and dihydi opyran systems,the data are still very scarce. The intermediate formation of pyrans valence-isomeric with unsaturated carbonyl compounds in the pyridine syntheses based on reactions of ammonia with aldehydes or ketones, advocated by various authors (cf. Section II,B,2,f), is still rather speculative. (See also Section II,B,2,e for the valence isomerism of 5-chloro-2,4-dienones with pyrylium chlorides.)... 

The 6-endo activated epoxy alcohol cyclization process was also expected to play a central role in the annulation of pyran ring G of the natural product (see Scheme 22). Silylation of the free secondary hydroxyl group in compound 131 furnishes, after hydrobora-tion/oxidation of the double bond, compound 132. Swern oxidation of alcohol 132 produces an aldehyde which reacts efficiently with (ethoxycarbonylethylidene)triphenylphosphorane in the presence of a catalytic amount of benzoic acid in benzene at 50 °C, furnishing... 

The chemistry of pyrans and their heteroanalogs has developed significantly since 1983, when it was first reviewed by one of the authors (83AHC145). To avoid undue length to this article, only the titled hetero-pyrans are treated and the discussion of the 1-oxygen analogs will be published in the future. 

Benz Derivatives of Pyrans, Pyrones, and Their Sulfur Analogues. 298... 

Inverse Diels-Alder Reactions. Synthesis of Pyranes... 

At least two derivatives of pyran have been used for the primary synthesis of quinoxalines. Thus o-phenylenediamine (390) and 6-(p-methoxyphenyl)-6-methyl-5,6-dihydro-2//-pyran-2,5-dione (391) in methylene chloride at 20°C open to the air for 48 h gave 3-[2-hydroxy-2-(p-methoxyphenyl)propionyl]methyl-3,4-dihydro-... 

Both the mode and site of nucleophilic attack of pyran-2-ones by alkoxides is influenced by the counter ion such that a variety of products can be obtained. In particular, chelation effects play a significant role <96JCS(P1)2715>. 

Enynes 71 react with aldehydes 61 in the presence of the [Ni(COD)J/SIPr catalytic system to afford two distinct products 72 and 73 (Scheme 5.20) [20b], The enone 72 is derived from aldehyde addition with the alkyne moiety while the adduct 73 arises from the aldehyde addition with the alkene moiety. The product distribution is dependent on the substituent on either the alkyne or alkene moieties. The reaction between 71 and ketones 74 led to the unprecedented formation of pyrans 75 (Scheme 5.20). The reaction showed to be highly regioselective in aU the cases, the carbonyl carbon was bound to the olefin. 

The [4 + 2] cycloaddition of enones and electron-rich olefins is a well-known method for the synthesis of pyrane derivatives [45]. Methylenecyclo-alkanediones [46] have also been used extensively for this purpose. 

Ring contractions of pyran derivatives are occasionally valuable. The contraction of 3-halo-2-pyrones to 2-furoic acids under the influence of alkali has been studied and the conditions defined.58112113 The method is adaptable to the preparation of 3-furoic acid via furan-2,4-dicarboxylic acid58 and of 3,4,5-triphenylfuran-2-carboxylic acid.113 Another ring contraction involving halides is the conversion of 4-chloromethylpyrylium salts into furylmethyl ketones as indicated in Scheme 21.114 Pyridine oxides may be transformed with unexpected ease into furans through treatment with a thiol (Scheme 22).115... 

Increasing use is being made of pyran syntheses based upon [4 + 2] cycloadditions of carbonyl compounds. The appropriate unsaturated aldehyde with ethyl vinyl ether yields 53 with peracids this affords an epoxide that undergoes ring contraction to the aldehyde 54 (Scheme 23) and rhodium catalyzed decarbonylation affords the required 3-alkylfuran with the optical center intact.116 Acetoxybutadiene derivatives add active carbonyl compounds giving pyrans that contract under the influence of acids to give... 

An example illustrating the synthesis of condensed oxepins by the cobalt-catalyzed reaction of bistrimethylsilylacetylene with a hexa-l,5-diyne derivative is shown in Scheme 175.234 This type of process has been discussed earlier in the context of pyran synthesis (see Scheme 158 in Section V,B,2). 

The cyclization of y -hydroxy ketones is useful for the formation of pyrans,306,403 both directly and via rearrangement, as illustrated in Eq. 231.153 As with their acyclic counterparts, these cyclizations also occur with the silyl ethers of the hydroxy ketones where Et3SiH/BiBr3 is used with the TBS and TES ethers.342,404 A methyl thiomethyl ether is also capable of undergoing the reductive cyclization 405 In like manner, 1,4-diols and e-hydroxy ketones provide oxepanes, with I ds Si H or PhMe2SiH/TMSOTf being especially effective (Eqs. 232 and 233).336,406 The trimethylsilyl ether of the alcohol also provides the oxepane.306... 

Connors and Jozwiakowski have used diffuse reflectance spectroscopy to study the adsorption of spiropyrans onto pharmaceutically relevant solids [12]. The particular adsorbants studied were interesting in that the spectral characteristics of the binary system depended strongly on the amount of material bound. As an example of this behavior, selected reflectance spectra obtained for the adsorption of indolinonaphthospiropyran onto silica gel are shown in Fig. 1. At low concentrations, the pyran sorbant exhibited its main absorption band around 550 nm. As the degree of coverage was increased the 550 nm band was still observed, but a much more intense absorption band at 470 nm became prominent. This secondary effect is most likely due to the presence of pyran-pyran interactions, which become more important as the concentration of sorbant is increased. 

Compounds are generally classified according to their fully unsaturated parent compound (but see below). Thus substituted, partially saturated, and fully saturated derivatives of, for example, pyrrole are all indexed under pyrrole. Benzo and similar derivatives are included under the most unsaturated parent system (e.g., quinoline, thienofuran, etc.). For any given heterocyclic parent only one indicated hydrogen isomer appears in the text, typically the most stable or the lowest numbered form thus all instances of pyran, whether of the 2H- or 4H-form, are indexed under 2H-pyran. The charges and additional valences for any heterocyclic parent structure are not indicated. 

Zirconocene-catalyzed kinetic resolution of dihydrofurans is also possible, as illustrated in Scheme 6.8 [18]. Unlike their six-membered ring counterparts, both of the heterocycle enantiomers react readily, albeit through distinctly different reaction pathways, to afford — with high diastereomeric and enantiomeric purities — constitutional isomers that are readily separable (the first example of parallel kinetic resolution involving an organome-tallic agent). A plausible reason for the difference in the reactivity pattern of pyrans and furans is that, in the latter class of compounds, both olefmic carbons are adjacent to a C—O bond C—Zr bond formation can take place at either end of the C—C 7T-system. The furan substrate and the (ebthi)Zr-alkene complex (R)-3 interact such that unfavorable... 

Lozano and Barba [82] electrolyzed 2-chloro-2-phenylacetyl chloride at mercury in methylene chloride and obtained derivatives of pyran-2-one and pyran-4-one, where R is H and C6H5CH2CO, respectively, at high and low current density (Scheme 6). In later work [83], the same workers reduced 2-bromo-2,2-diphenylacetyl bromide in methylene dichloride saturated with hydrogen sulfide gas three sulfur-containing... 

Scheme 39 Cathodic dimerization with subsequent disulfide elimination of pyran-4-thiones.

The common anomers have either a five- or a six-membered ring that contains an oxygen atom. A six-membered ring is a derivative of pyran therefore, the monosaccharide is a pyranose. A five-membered ring is a derivative of furan. 

NMR spectroscopy on nuclei in 2-aminopyrans, in many cases, fail to report shifts with a reference, or are assigned inaccurately (86H(24)935). Some examples of chemical shifts and references are given below the data for pyran 19 have been proven by the COSY technique (02X953). One paper (85MI2) was devoted to a comparative analysis of the spectra of pyrans 16, 17, as well as of those of a 2,6-dimethyl-4H-pyran analog. 

The mixture composition depends strongly on the Et0H H20 ratio, while the highest yields of pyran have been achieved in absolutized ethanol. Formation of 6-ethoxydihydropyran 53 possibly can be attributed to the influence of the CF3 group, which is a very strong acceptor and its presence in carbonyl compounds promotes acetal formation. 

When a 4-pyridyl substituent was used as an acceptor, the yield of pyran 62 was moderate (02CHE251) (Scheme 12). 

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