Alkenes reviews

Hydrogen activation precedes the coordination of the alkene. Reviews on hydrogen activation in relation to homogeneous catalysis are available.43,44 General reviews on homogeneous hydrogenation are listed at the end of Section 61.2.2. 

Nitrosochlorination of alkenes, review 23, 537 suppl. 24 Nitroso compound dimers s. Azo N,N -dioxides... 

One great advantage of this hydroboration-oxidation sequence is that it provides a route to alcohols that cannot be obtained by the acid-catalyzed hydration of alkenes (review eq. 3.13). 

For a discussion of pi bonds and bonding in alkenes, review Section 3.4. 

Alkenes. —Reviews on Ziegler-Natta catalysis and the stereoregular and sequence-regular polymerization of butadiene have been published and the stereoselective oligomerizations of isoprene by lithium and palladium catalysts have been compared. Semi-empirical MO calculations suggest that Ziegler-Natta polymerization proceeds via a bis-alkene complex and a metallacyclo-pentane intermediate. ... 

In the reaction of a substituted ylide (r CH—PPh ) with an aldehyde R CHO, a stereochemical problem arises. Much work has been carried out in order to achieve control of either cis- or rrans-alkene formation. This work has been reviewed several times with always changing viewpoints (A. Maercker, 1965 L.D. Bergelson, 1964 M. Schlosser, 1970 H. Best-mann, 1979). 

The structure of ethylene and the orbital hybridization model for its double bond were presented m Section 2 20 and are briefly reviewed m Figure 5 1 Ethylene is planar each carbon is sp hybridized and the double bond is considered to have a a component and a TT component The ct component arises from overlap of sp hybrid orbitals along a line connecting the two carbons the tt component via a side by side overlap of two p orbitals Regions of high electron density attributed to the tt electrons appear above and below the plane of the molecule and are clearly evident m the electrostatic potential map Most of the reactions of ethylene and other alkenes involve these electrons... 

Among the appHcations of lower valent titanium, the McMurry reaction, which involves the reductive coupling of carbonyl compounds to produce alkenes, is the most weU known. An excellent review of lower valent titanium reactions is available (195). Titanium(II)-based technology is less well known. A titanium(II)-based complex has been used to mediate a stetio- and regio-specific reduction of isolated conjugated triple bonds to the corresponding polyenes (196). 

The most important oxirane syntheses are by addition of an oxygen atom to a carbon-carbon double bond, i.e. by the epoxidation of alkenes, and these are considered in Section 5.05.4.2.2. The closing, by nucleophilic attack of oxygen on carbon, of an OCCX moiety is dealt with in Section 5.05.4.2.1 (this approach often uses alkenes as starting materials). Finally, oxirane synthesis from heterocycles is considered in Section 5.05.4.3 one of these methods, thermal rearrangement of 1,4-peroxides (Section 5.05.4.3.2), has assumed some importance in recent years. The synthesis of oxiranes is reviewed in (B-73MI50500) and (64HC(19-1U). 

Electron deficient carbon-carbon double bonds are resistant to attack by the electrophilic reagents of Section 5.05.4.2.2(t), and are usually converted to oxiranes by nucleophilic oxidants. The most widely used of these is the hydroperoxide ion (Scheme 79). Since epoxidation by hydroperoxide ion proceeds through an intermediate ct-carbonyl anion, the reaction of acyclic alkenes is not necessarily stereospecific (Scheme 80) (unlike the case of epoxidation with electrophilic agents (Section 5.05.4.2.2(f)) the stereochemical aspects of this and other epoxidations are reviewed at length in (B-73MI50500)). 

For a review of synthetic methods applicable to trisubstituted alkenes see J. Faulkner, Synthe.ais, 175 (1971). 

The photochemical cycloadditions of alkenes and alkynes with aromatic compounds have received by far the most attention. Yields of [2+2] cydoadducts can be good, but reaction times are often long and secondary rearrangement products are common [139, 140, 141,142, 143,144, 145,146] (equations 63-65). The pioneering mechanistic and synthetic work on aromatic photocycloadditions has been reviewed [147],... 

Before beginning a detailed discussion of alkene reactions, let s review briefly some conclusions from the previous chapter. We said in Section 5.5 that alkenes behave as nucleophiles (Lewis bases) in polar reactions. The carbon-carbon double bond is electron-rich and can donate a pair of electrons to an electrophile (Lewis acid), for example, reaction of 2-methylpropene with HBr yields 2-bromo-2-methylpropane. A careful study of this and similar reactions by Christopher Ingold and others in the 1930s led to the generally accepted mechanism shown in Figure 6.7 for electrophilic addition reactions. 

One of the most striking differences between conjugated dienes and typical alkenes is in their electrophilic addition reactions. To review briefly, the addition of an electrophile to a carbon-carbon double bond is a general reaction of alkenes (Section 6.7). Markovnikov regiochemistry is found because the more stable carbo-cation is formed as an intermediate. Thus, addition of HC1 to 2-methylpropene yields 2-chloro-2-methylpropane rather than l-chloro-2-methylpropane, and addition of 2 mol equiv of HC1 to the nonconjugated diene 1,4-pentadiene yields 2,4-dichloropentane. 

Fluorinated alkenes and alkynes are highly activated toward nucleophilic attack and reaction with bifunctional nucleophiles is a fruitful area for the synthesis of heterocycles. A review on perfluoroalkyl(aryl)acety-lenes contains many examples (91RCR501). 

The synthesis of 2-chloro-2,3,3-trifluorocyclobutyl acetate illustrates a general method of preparing cyclobutanes by heating chlorotrifluoroethylene, tetrafluoroethylene, and other highly fluorinated ethylenes with alkenes. The reaction has recently been reviewed.11 Chlorotrifluoroethylene has been shown to form cyclobutanes in this way with acrylonitrile,6 vinylidene chloride,3 phenylacetylene,7 and methyl propiolate.3 A far greater number of cyclobutanes have been prepared from tetrafluoroethylene and alkenes 4,11 when tetrafluoroethylene is used, care must be exercised because of the danger of explosion. The fluorinated cyclobutanes can be converted to a variety of cyclobutanes, cyclobutenes, and butadienes. 

The first step of this procedure illustrates a general reaction, the addition of allenes to alkenes to form methylenecyclobutanes. The reaction has been reviewed recently.7... 

We will focus on the development of ruthenium-based metathesis precatalysts with enhanced activity and applications to the metathesis of alkenes with nonstandard electronic properties. In the class of molybdenum complexes [7a,g,h] recent research was mainly directed to the development of homochi-ral precatalysts for enantioselective olefin metathesis. This aspect has recently been covered by Schrock and Hoveyda in a short review and will not be discussed here [8h]. In addition, several important special topics have recently been addressed by excellent reviews, e.g., the synthesis of medium-sized rings by RCM [8a], applications of olefin metathesis to carbohydrate chemistry [8b], cross metathesis [8c,d],enyne metathesis [8e,f], ring-rearrangement metathesis [8g], enantioselective metathesis [8h], and applications of metathesis in polymer chemistry (ADMET,ROMP) [8i,j]. Application of olefin metathesis to the total synthesis of complex natural products is covered in the contribution by Mulzer et al. in this volume. 

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