Heterocyclics pyrans

The cyclic form of glucose is termed glucopyra-nose, since the new ring system is a reduced form of the oxygen heterocycle pyran. Nucleophilic attack onto the planar carbonyl may occur from either of its two faces, generating two different stereochemistries at this new chiral centre, designated as a or p. This new chiral centre is termed the anomeric centre. Since there are other chiral centres in the molecule, the mixture of a- and -anomeric forms is not a racemate, but a mixture of diastereoisomers (see Section 3.4.4). The mixture does not contain 50% of each anomer (see below). Although both forms are produced, the form with the equatorial hydroxyl is thermodynamically favoured (see Section 3.3.2). 

There are thousands of phenolic compounds in plants, divided into several classes according to their structures. The simplest structures are Cs, Q-Q ben-zenic compounds such as benzoic acids (Figure 16.1a), and C6-C3-C6 compounds composed of two benzenic rings (A and B) and a heterocyclic pyranic ring C, characteristic of flavonoids (Figure 16.1c). The more complex are in general polymers of these structures. 

The cyclic hemiacetal that has a five-membered ring is called a furanose. This name is derived from that of tire five-membered, oxygen-containing heterocyclic compound fu-ran. The hemiacetal with a six-membered ring is known as a pyranose after the heterocycle pyran. 

If the name of a carbohydrate is exactly to define a particular structure, it must indicate ring size. Following a suggestion made by Haworth, carbohydrates are named to show their relationship to one of the heterocycles pyran or furan. 

Products of the phenylpropanoid pathway. These compounds, commonly referred to as polyphenols, are derived from cinnamic acid and include the xanthones and flavonoids. The basic structural unit of the flavonoid family (Fig. 1) comprises two benzene rings linked through a heterocyclic pyran or pyrone ring (C ring) variations in the C ring and the extent of hydroxylation define the major classes [4]. 

The interaction between benz aldehyde and acetic anhydride in the presence of sodium acetate results into the formation of the heterocyclic pyran ring to give coumanin in addition to a mole each of acetic acid and water as products of reaction. 

These names come from the names of the oxygen heterocycles pyran and furan + ose-. 

The six-membered cyclic form of most monosaccharides is the preferred structure. These structures are called pyranose forms after the six-membered oxygen heterocycle pyran. The formula at the extreme left of eq. 16.3 is more completely named a-D-glucopyranose, with the last part of the name showing the ring size. 

Zborowski, K., R. Grybos, and L.M. Proniewicz. 2005. Theoretical studies on the aromaticity of selected hydroxypyrones and their cations and anions. Part 1 Aromaticity of heterocyclic pyran rings. J. Phys. Org. Chem. 18 250-254. 

The basic stractural feamre of isoflavonoids is two benzene rings linked through a heterocyclic pyrane ring at position 3. The most abundant isoflavonoids are genistein... 

Chemically, all flavonoids possess a Ce—C3—Ce backbone, with two benzene rings (A and B) connected via a heterocyclic pyrane or a pyrone ring (C) (Rgure 4.1). 

These structures were called pyranoses after the six-membered heterocycle, pyran, with oxygen in the ring. 

There are several examples of the formation of pyridazines from other heterocycles, such as azirines, furans, pyrroles, isoxazoles, pyrazoles or pyrans and by ring contraction of 1,2-diazepines. Their formation is mentioned in Section 2.12.6.3.2. 

Oxidation of 4H-pyran-4-thiones with thallium(III) trifluoroacetate was used in the one pot synthesis of l,6-dioxa-6n-thiapentalenes, a hypervalent heterocyclic system [57] (equation 27)... 

Steroids with 0-heterocyclic fragments (pyrans and 0-macroheterocycles) as bioactive metabolites from echinoderms andporifera 97G771. 

Unusual reactions occur between diazomethane and heterocyclic thiocarbonyl compounds. For example, pyran-4-thiones give methylene ethers of 1,2-dimercaptans formed by dimerization (cf. 115 —>116). 4-Thioflavones and 4-thiochromones react similarly. 

Transformations of 5,6-dihydro-2//-pyrans 8 into the corresponding 3,4-dihydro-2//derivatives 9 under basic conditions (88KGS291 98TL2025), as well as the reverse conversion under irradiation [97H(46)451], have been explained by the intermediate formation of electron-delocalized heterocyclic systems, giving rise to two possible isomers. 

A closely related oxygenated heterocyclic system devoid of acidic groups interestingly shows quite different biological activity. Thus, condensation of the benzofuran hydroxyketone 66 with ethyl thiomethyl acetate (67) probably proceeds initially by formation of the acylation product 68. Intramolecular dehydration leads to formation of a pyran ring. There is thus obtained the hypo-cholesterolemic agent timefurone (69) [14],... 

The preparation of 5-ACETYL-l,2,3,4,5-PENTAMETHYLCYCLO-PENTADIENE is of value in the synthesis of pentamethyleyclo-pentadiene and many pentamethylcyclopentadienyl metal carbonyl derivatives that are more soluble in organic solvents than those derived from cyclopentadiene. Simple preparations of 5,6-DIHYDRO-2-PYRAN-2-0NE and 2-//-PYRAN-2-ONE make these hitherto rather inaccessible intermediates available for cycloaddition and other reactions. The already broad scope of the Michael reaction has been widened further by including an efficient preparation of ETHYL (E)-3-NITROACRYLATE. Workers in the field of heterocyclic chemistry will find a simplified method for the preparation of 2,3,4,5-TETRA-HYDROPYRIDINE of help. 

Over the years, many spiropyran structures have been prepared. The pyran component consists of benzopyran or naphthopyran and the heterocyclic part consists of indoline, benzothiazoline, benzoxazoline, benzoselen-azoline, phenanthridine, acridine, quinoline, benzopyran, naphthopyran, xanthene, benzodithiole, benzoxathiole, and saturated heterocyclic rings such as pyrolidine and thiazolidine. 

An example of thione coordination is demonstrated with the thiocarbonyl donor ligand 2,6-dimethyl-4H-pyran-4-thione, that gives a complex with zinc chloride of the form ZnL2Cl2-The crystal structure shows the zinc is tetrahedrally coordinated by two chloride and two sulfur donors and the compound was further studied by 3H NMR and IR spectroscopy.573 Both monomeric and dimeric heterocyclic thione complexes have been formed with zinc.5 4,575... 

Pyrano- and thiopyranopyridines and their aza analogues fused to a five-membered heterocycle 12.17.3.1,5(i) Pyran or thiopyran as the outer ring... 

The l,3-oxazin-2-ones and 1,3-oxazine-2-thiones previously synthesized were used to prepare various N- and O-heterocyclic systems fused with 1,3-oxazine rings.172 For example, furan-l,3-oxazin-2-one or furan-l,3-oxazine-2-thiones (190a,b) and pyran-l,3-oxazin-2-ones or pyran-l,3-oxazine-2-thiones (190c,d) were prepared in very good yields, ranging from 83% to 90%, by montmorillonite K-10 clay-catalyzed cyclodehydration of 189a,b and 189c,d, respectively (Scheme 35). 

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. 

The high levels of enantioselectivity obtained in the asymmetric catalytic carbomagnesa-tion reactions (Tables 6.1 and 6.2) imply an organized (ebthi)Zr—alkene complex interaction with the heterocyclic alkene substrates. When chiral unsaturated pyrans or furans are employed, the resident center of asymmetry may induce differential rates of reaction, such that after -50 % conversion one enantiomer of the chiral alkene can be recovered in high enantiomeric purity. As an example, molecular models indicate that with a 2-substituted pyran, as shown in Fig. 6.2, the mode of addition labeled as I should be significantly favored over II or III, where unfavorable steric interactions between the (ebthi)Zr complex and the olefmic substrate would lead to significant catalyst—substrate complex destabilization. 

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