Carbonylation of Alkenes and Dienes

The first example for carbonylation reaction of olefins, discovered by Otto Roelen and patented in 1938, was the addition of carbon monoxide and dihydrogen to an olefin double bond in the presence of transition metal catalysts (Equation 7.1). 

Replacing hydrogen by water yields carboxylic adds and the modified readion is named hydrocarboxylation (Equation 7.2). Another example of synthesis taking place with very similar mechanism is hydroesterification (also termed hydroalkoxy-carbonylation) that uses alcohol as hydrogen source, yielding esters as produds (Equation 7.3). 

In this chapter, some examples of the reactions depided in Equations 7.1-7.3 and some illustrations of one-pot reactions mainly based on hydroformylation will be reviewed. The scientific literature is covered from 2002 till April 2007. 

Modem Carbonylation Methods. Edited by Uiszlo KoIIar 

Copyright 2008 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim 

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Photocycloaddition of Alkenes and Dienes. Photochemical cycloadditions provide a method that is often complementary to thermal cycloadditions with regard to the types of compounds that can be prepared. The theoretical basis for this complementary relationship between thermal and photochemical modes of reaction lies in orbital symmetry relationships, as discussed in Chapter 10 of Part A. The reaction types permitted by photochemical excitation that are particularly useful for synthesis are [2 + 2] additions between two carbon-carbon double bonds and [2+2] additions of alkenes and carbonyl groups to form oxetanes. Photochemical cycloadditions are often not concerted processes because in many cases the reactive excited state is a triplet. The initial adduct is a triplet 1,4-diradical that must undergo spin inversion before product formation is complete. Stereospecificity is lost if the intermediate 1,4-diradical undergoes bond rotation faster than ring closure. 

The photocatalytic hydrogenation of alkenes and dienes by Group 6 metal carbonyls has been investigated in LNG solvents [15]. Photolysis of trans-[M(C0)4(C2H4)2] (M = Cr, Mo, W) in liquid xenon doped with H2 leads to formation of mer-[M(CO)3(C2H4)2(q -H2)] and ds-[M(CO)4(C2H4)(q -H2)]. The q -H2 complexes for M = Cr and Mo are much less stable than those for M = W. The evidence supported -coordination of H2 rather than oxidative addition to give dihy-... 

Other additions, such as addition of alkyl halides and carbonyl compounds, are discussed in Chapter 5, whereas Chapter 7 covers addition reactions involving carbon monoxide (hydroformylation, carboxylations). Hydrogen addition is discussed in Chapter 11. The nucleophilic addition of organometallics to multiple bonds is of great significance in the anionic polymerization of alkenes and dienes and is treated in Chapter 13. 

Alkenes can be transformed to carbonyl compounds through the oxidation of the vinylic carbon atom. A special case of vinylic oxidation is acetoxylation of alkenes and dienes. 

The versatility of these [4+2] heterocyclization reactions is a consequence of the wide range of ene and diene components which can be used. In addition to alkenes and alkynes functioning as ene components, a variety of heterodienophiles is available such as electron-deficient imines (e.g. equation 89), nitriles e.g. equation 90), electrophilic carbonyl compounds (e.g. equation 91), thiocarbonyl compounds (e.g. equation 92), singlet oxygen (e.g. equation 93), nitroso compounds (e.g. equation 94), sulfenylsulfonamides (e.g. equation 95) and azo compounds (e.g. equation 96). Many of these reactions proceed with excellent regioselectivity and stereoselectivity, probably because in many instances they involve... 

Although the reaction of i-Bu2Si with nitriles, isocyanides, carbonyl compounds and heterodienes had been studied earlier, the interaction with alkenes and dienes is new. Siliranes are obtained with alkenes, as predicted (equation 17)48. 

More recently, Pfaltz has reported high enantioselectivities for the cyclopropanation of monosubstituted alkenes and dienes with diazo carbonyl compounds using chiral (semicorrinato)copper complexes (P-Cu) (23-25), and Evans, Masamune, and Pfaltz subsequently discovered exceptional enantioselectivities in intermolecular cyclopropanation reactions with the analogous bis-oxazoline copper complexes (26-28). With the exception of the chiral (camphorquinone dioximato)cobalt(II) catalysts (N-Co) reported by Nakamura and coworkers (29,30), whose reactivities and selectivities differ considerably from copper catalysts, chiral complexes of metals other than copper have not exhibited similar promise for high optical yields in cyclopropanation reactions (37). 

Both disubstituted alkynes (Chapter 3.3, this volume) and isolated terminal double bonds may be reduced by alkali metals in NH3, but isolated double bonds are usually stable to these conditions. However, 16,17-secopregnanes (10 equation 8) afford mixtures of cyclization products (11) and (12) in 61% to 80% yield with Na naphthalenide-THF, Na-NHs-THF, Na-THF or Li-NHs-THF. With Na-NHa-THF-r-butyl alcohol, a 91% yield of a 72 28 mixture of (11) (12) (R = Me) is obtained. This type of radical cyclization of alkenes and alkynes under dissolving metal reduction conditions to form cyclopentanols in the absence of added proton donors is a general reaction, and in other cases it competes with reduction of the carbonyl group. Under the conditions of these reactions which involve brief reaction times, neither competitive reduction of a terminal double bond nor an alkyne was observed. However, al-lenic aldehydes and ketones (13) with Li-NHs-r-butyl alcohol afford no reduction products in which the diene system survives. ... 

Reviews are available on the palladium-catalyzed carbonylation of organic halides, dienes and mixtures of alkenes and organic halides. ... 

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