Unsaturated substrates

Miscellaneous Unsaturated Substrates. Exposure of l,l -bis(trans-2-cyanovinyl)ferrocene to a mixture of two equivalents of triethylsilane and 320 equivalents of trifluoroacetic acid at 50° for three hours gives a product with the carbon-carbon double bonds reduced in 83% yield, but leaving the nitrile groups intact (Eq. 122).179 

Treatment of a chloroform or dichloromethane solution of l-bromo-2,2-diphen-ylethene or l-bromo-2,2-bis(4/-methoxyphenyl)ethene with a slight excess of triethylsilane and a 9- to 10-fold excess of TFA gives the corresponding ethanes in 62% and 88% yields, respectively, after one hour at 0° (Eq. 123).184 

An interesting hydroiodination reaction occurs when a mixture of cyclohexene and triethylsilane in dichloromethane is treated with a mixture of bis(pyridine) iodonium tetrafluoroborate and tetrafluoroboric acid in diethyl ether (Eq. 125). A 50% yield of iodocyclohexane is produced after one hour at 20°.268 

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Gycloaddition Reactions. Isocyanates undergo cyclo additions across the carbon—nitrogen double bond with a variety of unsaturated substrates. Addition across the C=0 bond is less common. The propensity of isocyanates to undergo cycli2ation reactions has been widely explored for the synthesis of heterocycHc systems. Substrates with C=0, C=N, C=S, and C=C bonds have been found to yield either 2 + 2, 2 + 2 + 2, or 2 + 4 cycloadducts or a variety of secondary reaction products (2). 

Synthetic polymers are classified by their method of synthesis as either chain-growth or step-growth. The categories ate somewhat imprecise but nevertheless provide a useful distinction. Chain-growth polymers are produced by chain-reaction polymerization in which an initiator adds to a carbon-carbon double bond of an unsaturated substrate (a vinyl monomer) to yield a reactive inter-... 

The acyl phosphonates, acyl phosphine oxides and related compounds (e.g. 81. 82) absorb strongly in the near UV (350-400 nm) and generally decompose by rescission in a manner analogous to the benzoin derivatives.381"285 Quantum yields vary from 0.3 to 1.0 depending on structure. The phosphinyl radicals are highly reactive towards unsaturated substrates and appear to have a high specificity for addition v.v abstraction (see 3.4.3.2). 

Cyanoisopropyl radicals generally show a high degree of specificity in reactions with unsaturated substrates. They react with most monomers (c.g. S, MMA) exclusively by tail addition (Scheme 3.4). However, Bcvington et al.11 indicated that cyanoisopropyl radicals give ca 10% head addition with VAc at 60 °C and that the proportion of head addition increases with increasing temperature. 

Hydroxy radical and sulfate radical anion, though they may sometimes give rise to similar products, show quite different selectivity in their reactions with unsaturated substrates. In particular, the sulfate radical anion has a somewhat lower propensity for hydrogen abstraction than the hydroxyl radical. For example, the sulfate radical anion shows little tendency to abstract hydrogen from mcthacrylic acid.232... 

This reagent reacts with a,/3-unsaturated ketones to give kinetic products of exclusive 1,4-addition (2). With cyclic substrates, a strong preference for axial addition is observed, as is a susceptibility to steric hindrance. Transformation into the corresponding silylcuprate species permits conjugate addition to a wider variety of a,/3-unsaturated substrates (3,4). 

The cydopropanation reaction of an unsaturated substrate is one of the most important strategies to access three-membered ring derivatives. The use of Fischer carbene complexes to perform this kind of cyclisation has become an important tool in organic synthesis [4]. In the next few sections the most significant features of this chemistry are briefly described. 

The mechanisms so far considered can, in theory at least, operate on any type of saturated (or for that matter unsaturated) substrate. There are other mechanisms that are more limited in scope. 

Scheme 10 Reactions of FeXs with different unsaturated substrates...

Because organophosphorus compounds are important in the chemical industry and in biology, many methods have been developed for their synthesis [1]. This chapter reviews the formation of phosphorus-carbon (P-C) bonds by the metal-catalyzed addition of phosphorus-hydrogen (P-H) bonds to unsaturated substrates, such as alkenes, alkynes, aldehydes, and imines. Section 5.2 covers reactions of P(lll) substrates (hydrophosphination), and Section 5.3 describes P(V) chemistry (hydrophosphorylation, hydrophosphinylation, hydrophosphonylation). Scheme 5-1 shows some examples of these catalytic reactions. 

The reaction of P-H bonds with unsaturated substrates often proceeds without a metal catalyst [2]. In addition, add or base-catalyzed [3] as well as radical reactions [4] have been reported and extensively reviewed. Metal-catalyzed transformations like the ones described here, however, often offer improvements in rate, selectivity,... 

In comparison to related P(III) chemistry, metal-catalyzed additions of P-H bonds in P(V) compounds to unsaturated substrates have been studied in more detail, and several synthetically useful processes have been developed. In particular, the use of heterobimetallic BINOL-based catalysts allows asymmetric hydrophosphonylation of aldehydes and imines in high yield and enantiomeric excess. 

Metal-catalyzed additions of P(III)-H and P(V)-H bonds to unsaturated substrates have been studied much less than related additions of, for example, B-H or Si-H bonds [36]. Already, some synthetically useful processes have been developed, and further work is likely to produce additional useful transformations as well as more fundamental information on the mechanisms of these reactions. 

This book is divided in eight chapters and each of them is devoted to the state-of-the art of the homogeneously catalysed addition of E-H or E-E heteroelement bonds to unsaturated substrates with C=C, C=C and C=X functions (X = O, S). Em-... 

The discussion of the activation of bonds containing a group 15 element is continued in chapter five. D.K. Wicht and D.S. Glueck discuss the addition of phosphines, R2P-H, phosphites, (R0)2P(=0)H, and phosphine oxides R2P(=0)H to unsaturated substrates. Although the addition of P-H bonds can be sometimes achieved directly, the transition metal-catalyzed reaction is usually faster and may proceed with a different stereochemistry. As in hydrosilylations, palladium and platinum complexes are frequently employed as catalyst precursors for P-H additions to unsaturated hydrocarbons, but (chiral) lanthanide complexes were used with great success for the (enantioselective) addition to heteropolar double bond systems, such as aldehydes and imines whereby pharmaceutically valuable a-hydroxy or a-amino phosphonates were obtained efficiently. 

H. Kuniyasu continues the discussion of the activation of group 16 element bonds with an overview on S(Se)-X additions to unsaturated substrates. For some time, it... 

Early work in the field of asymmetric hydroboration employed norbornene as a simple unsaturated substrate. A range of chiral-chelating phosphine ligands were probed (DIOP (5), 2,2 -bis(diphenyl-phosphino)-l,l -binaphthyl (BINAP) (6), 2,3-bis(diphenylphosphino)butane (CHIRAPHOS) (7), 2,4-bis(diphenylphosphino)pentane (BDPP) (8), and l,2-(bis(o-methoxyphenyl)(phenyl)phos-phino)ethane) (DIPAMP) (9)) in combination with [Rh(COD)Cl]2 and catecholborane at room temperature (Scheme 8).45 General observations were that enantioselectivities increased as the temperature was lowered below ambient, but that variations of solvent (THF, benzene, or toluene) had little impact. 

Alternatively, l,3-dithiol-2-ones have been obtained by reacting di-isopropylxanthogen disulfide with unsaturated substrates, such as disubstituted alkynes R2C2, in the presence of AIBN (azoisobutyrylnitrile), a radical initiator.78 Finally, vinylene dithiocarbonates can be obtained by reacting mer-cury(II) acetate with the corresponding trithiocarbonates, generated by reaction of electrophilic alkynes with ethylene trithiocarbonate.79 Analogously,... 

Scheme 7 comprises the following patterns First, a metallacycle gives rise to ketones by CO insertion and reductive elimination. Next, a nickel hydride inserts an unsaturated substrate L, followed by CO. The acyl intermediate can give rise to reductive elimination with formation of acyl halides or acids and esters by hydrolysis, or it can insert a new ligand with subsequent reductive elimination as before. Alternatively, there may be a new insertion of carbon monoxide with final hydrolysis. Third, an intermediate R—Ni—X is formed by oxidative addition. It can react in several ways It can insert a new ligand L, followed by CO to give an... 

Oxidative addition of the silyl species to nickel is followed by insertion of unsaturated substrates. Zero-valent nickel complexes, and complexes prepared by reducing nickel acetylacetonate with aluminum trialkyls or ethoxydialkyls, and in general Ziegler-Natta-type systems, are effective as catalysts (244, 260-262). Ni(CO)4 is specific for terminal attack of SiHCl3 on styrene (261). 

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