Unsaturated system examples

Conjugate addition of a carbon-nucleophile to an a,(3-unsaturated system. Example 1... 

Lewis acid-mediated addition of allylsilanes to carbon nucleophiles. Also known as the Hosomi-Sakurai reaction. The allylsilane will add to the carbonyl compound directly if it is not part of an a,P-unsaturated system (Example 2), giving rise to an alcohol. 

Many of these reactions occur in the course of synthesis of fully or partly unsaturated products after initial ring closure, giving rise to more unsaturated systems, e.g. in the pyrido[2,3-pipemidic acids (Section 2.15.4.1) and their derivatives, e.g. (16a) -> (17) (74JAP(K)7444000). Examples are also found in the pyrido[3,2-[Pg.205]

The first example of a cycloaddition reaction of a multiple bond to a diene was reported in 1917 Surprisingly, it was found that benzal azine adds to 2 equivalents of several unsaturated systems, when offered in excess, to yield bicyclie compounds. This reaction was named criss-cross" cycloaddition [190], Exploitation of the preparative potential of criss-cross cycloaddition began only in the early 1970s, when hexafluoroacetone azine became available on a larger scale [191,192] The study of this reaction proved to be an impetus tor the development of azine chemistry [183, 193]... 

The simplest description of an excited state is the orbital picture where one electron has been moved from an occupied to an unoccupied orbital, i.e. an S-type determinant as illustrated in Figure 4.1. The lowest level of theory for a qualitative description of excited states is therefore a Cl including only the singly excited determinants, denoted CIS. CIS gives wave functions of roughly HF quality for excited states, since no orbital optimization is involved. For valence excited states, for example those arising from excitations between rr-orbitals in an unsaturated system, this may be a reasonable description. There are, however, normally also quite low-lying states which essentially correspond to a double excitation, and those require at least inclusion of the doubles as well, i.e. CISD. 

Additions include the attachment of two univalent atoms or groups (called addends) to an unsaturated system, e. g., to olefins, carbonyl groups, aromatic systems, carbenes, etc. (Rule 2.1). For example, the addition of hydrocyanic acid to the car-... 

The unconventional structure of fulvenes with a unique C=C bond conjugation leads to unusual cycloaddition reactions with other unsaturated systems. For example, alkenylcarbene complexes react with fulvenes leading to indanone or indene derivatives which can be considered as derived from a [6S+3C] cycloaddition process [118] (Scheme 72). The reaction pathway is well explained by an initial 1,2-addition of the fulvene to the carbene carbon followed by [1,2]-Cr(CO)5-promoted cyclisation. 

On the other hand, groups that have a multiple-bonded electronegative atom directly connected to an unsaturated system are —A/ groups. In such cases, we can draw canonical forms in which electrons have been taken from the unsaturated system into the group, for example. 

The general term metallation describes that process in which reaction of an unsaturated system with a metal or an electrophilic metal salt results in formation of an unsaturated organometallic compound by formal replacement of a C—H bond by a C—metal bond, as for example in the mercuration of benzene (Scheme 3). The term oxymetallation is used to describe the... 

The utility of thallium(III) salts as oxidants for nonaromatic unsaturated systems is a consequence of the thermal and solvolytic instability of mono-alkylthallium(III) compounds, which in turn is apparently dependent on two major factors, namely, the nature of the associated anion and the structure of the alkyl group. Compounds in which the anion is a good bidentate ligand are moderately stable, for example, alkylthallium dicar-boxylates 74, 75) or bis dithiocarbamates (76). Alkylthallium dihalides, on the other hand, are extremely unstable and generally decompose instantly. Methylthallium diacetate, for example, can readily be prepared by the exchange reaction shown in Eq. (11) it is reasonably stable in the solid state, but decomposes slowly in solution and rapidly on being heated [Eq. (23)]. Treatment with chloride ion results in the immediate formation of methyl chloride and thallium(I) chloride [Eq. (24)] (55). These facts can be accommodated on the basis that the dicarboxylates are dimeric while the... 

Table 2-1 lists some examples of carboxylic acid imidazolides of various structures prepared by the use of A -carbonyldiimidazole (CDI), A -thiocarbonyldiimidazole (Im-CS-Im), and A -sulfinyldiimidazole (Im-SO-Im). Independent of the specific method applied, the data in Table 2-1 show that reasonable yields of imidazolides and diimidazolides are quite general, irrespective of various substituents and of steric factors. The rather mild reaction conditions also permit the formation of imidazolides of highly unsaturated systems. As a further advantage, it should be mentioned that almost all imidazolides are crystalline compounds, which can be conveniently handled. Melting points are therefore included for the imidazolides listed in Table 2—1. 

The intermolecular carbometallation reaction catalyzed by transition metals from groups 8 to 11 has been fully investigated during the last decade. Many examples have been reported in the literature concerning different metals in order to create C-C bonds. Overview of this powerful method will be given as exhaustively as possible and carbometallation reactions will be classified according to unsaturated systems. 

In this section, we shall examine the various approaches by which crown compounds that have their chiral elements associated in some way with fused ring systems can be constructed. A selection of the wide and growing range of saturated chiral diols—many of them derived finom readily available carbohydrates—which have been incorporated, as relatively inexpensive sources of chirality, into crown ether derivatives are displayed in Figure IS. It may be noted that the saturated chiral diols rely for their chirality on centers of the classical type (C abcd)—not so the chiral dihydroxy compounds associated with the unsaturated systems listed in Figure 16. These examples reveal that axes and planes of chirality join with less conventional chiral centers (C aaaa) in being sources of chirality in optically active crown ethers. 

A number of seven-membered rings containing more than four sulfur atoms are known for example, the unsaturated system (596) and its benzo analogue can be prepared in good yields by the reaction of dichlorotrisulfane (S3CI2) with ds-mercaptoethylene or 1,2-benzenedithiol respectively (71TL2125). Lenthionine (597) and hexathiepane are both found in species of mushroom and can be prepared by reactions of dichloromethane, sodium sulfide and methylene chloride (66TL573). 

This weak transition is due to the promotion of an electron from the non-bonding molecular orbital n to an anti-bonding tt orbital. This transition is usually observed in molecules that contain a heteroatom as part of an unsaturated system. The most common of these bands corresponds to the carbonyl band at around 270 to 295 nm, which can be easily observed. The molar absorption coefficient for this band is weak. The nature of the solvent influences the position of absorption bands because the polarity of the bond is modified during absorption. For example, ethanal Amax = 293 nm (e = 12 in ethanol as solvent). 

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