Internal reaction scheme

The Ciamician-Dennstedt reaction can be thought of as the complement to the Reimer-Tiemann reaction (Scheme 8.3.2). The first step of both reactions is cyclopropanation of one of the carbon-carbon double bonds of a pyrrole with a dichlorocarbene, resulting in intermediate 3. The Ciamician-Dennstedt reaction results from cleavage of the internal C-C bond and elimination of chloride (path a), while the Reimer-Tiemann reaction results from cleavage of the exocyclic bond, and subsequent hydrolysis of the dichloromethyl moiety to furnish aldehyde 5 (path b). 

In principle, reaction schemes similar to that given in the preceding paragraph may be developed for other comparable rate processes, for example spinel formation. However, Stone [27] has pointed out that, where the barrier phase is not an efficient ionic conductor, the overall reaction may be controlled by the movement of a single cation and anion. In addition, there is the probability that lattice imperfections (internal surfaces, cracks, leakage paths [1172], etc.) may provide the most efficient route to product formation.]... 

The anti-Markovnikov product was formed with >95% regioselectivity at 35°C. The examples in Scheme 5-21, Eq. (1) show that cyano and hydroxyl functional groups are tolerated by the catalyst, and diphenylphosphine oxide can be added to both C=C bonds in a di-alkyne. The reaction also worked for internal alkynes (Scheme 5-21, Eq. 2). Unusual Markovnikov selectivity was observed, however, for 1-ethynyl-cyclohexene (Scheme 5-21, Eq. 3) [17]. 

Method 3 was modified to an internal standard method into Method 5 by changing the bonded phase and the mobile phase composition. Biphenyl was used as an internal standard added into the reaction. Aliquots were withdrawn, diluted with degassed acetonitrile, and analyzed according to Method 5. This internal standard method, Method 5, was helpful in the optimization of the desired ris-1,2/1,4 product of the key step of the LANA reaction (scheme 5). 

The reaction of triallylborane with silicon triyne 123 is interesting. A113B attacks both internal and external triple bonds giving rise to silole 124 and two heterocycles with bridgehead boron 125 and 126 in a 1 3 3 ratio as a result of competitive sequential reactions (Scheme 52). When 1,1-allylboration of the internal C C bond followed by intramolecular 1,1-vinyIboration takes place, the silole 124 is formed, while in another case 1,1-allylboration followed by a series of intramolecular 1,2-allylboration reactions leads to boron derivatives 125 and 126 <2002JOM(657)146>. 

Palladium-catalyzed cyclic carboxylation of dienes can be utilized for the synthesis of lactones.2 Polymer-supported Pd catalyst could also be used for this reaction (Scheme 42).61 The reaction is initiated by dimerization of two molecules of diene to give a bis-7r-allylpalladium intermediate such as 123. The incorporation of C02 takes place at the internal position of an allyl unit to afford the 7r-allylpalladium carboxylate 124 which, after reductive elimination/ cyclization, yields the (5-lactone 121 (Scheme 43). 

Fig. 18. Reaction scheme showing the various polyanions that can form upon acidification of [W04]2. Parentheses are used to distinguish internal H from external H where necessary. Question marks indicate tentative formulations. (Adapted with permission from Hastings, J. J., Howarth, O. W. J. Chem. Soc. Dalton Trans. 1992, 209-215.)...

The hydroformylation reaction that converts olefins into aldehydes is the largest volume homogeneous transition-metal catalyzed reaction used today. This reaction has been extensively studied and nowadays a number of efficient catalysts make it possible to control the regioselectivity of the reaction to give terminal or internal aldehydes (Scheme 1). 

Cobaloxime(I), electrochemically regenerated from chloro(pyridine)-cobaloxime (III) (232), has been employed as a mediator in the reductive cleavage of the C—Br bond of 2-bromoalkyl 2-alkynyl ethers (253), giving (254) through radical trapping ofthe internal olefin (Scheme 95) [390]. An interesting feature of the radical cyclization (253) (254) is the reaction in methanol, unlike the trialkyltin hydride-promoted radical reactions that need an aprotic nonpolar solvent. An improved procedure for the electroreductive radical cyclization of (253) has been attained by the combined use of cobaloxime(III) (232) and a zinc plate as a sacrificial anode in an undivided cell [391]. The procedure is advantageous in terms of the turnover of the catalyst and the convenience of the operation. 

Olefin isomerization reactions range from some of the most facile using acid catalysts to moderately difficult and, as components of more complex reaction schemes such as catalytic cracking, may be among the most common reactions in hydrocarbon processing. As stand-alone reactions, they are primarily used to shift the equilibrium between terminal and internal olefins or the degree of branching of the olefin. While olefin isomerization was considered for the production of MTBE, today stand-alone olefin isomerization processes are only considered for a few special situations within a petrochemical complex. 

In an analogous late-stage arylation approach, terminal alkyne 31 was envisioned as a versatile intermediate. Slow addition of 4-pentynoyl chloride to imine 3 and (n-Bu)3N at reflux (efficient condenser, 100°C, 12 h, 1 1 toluene heptane) afforded only trace amounts of 31. Reaction of 4-pentynoyl chloride with triethylamine in methylene chloride under preformed ketene conditions ( 78°C, 1 h), followed by addition of 3 and warming to — 10°C over 4 h, afforded a complex mixture of products. Since high-yield preparation of 31 remained elusive, access to internal alkynyl analogs (type 33) was accomplished by preassembly of the appropriate arylalkynyl acid substrate for the ketene-imine cycloaddition reaction (Scheme 13.9). 

The term chemical autopoiesis indicates the experimental implementation of autopoiesis in the chemistry laboratory. The most well known of these processes is the self-reproduction of micelles and vesicles. This has been discussed in the previous chapter, where the original idea of Francisco Varela and myself was to work with bounded systems that would produce their own components due to an internal reaction, respecting the scheme illustrated in Figure 8.3. We came up with the idea of using reverse micelles (refer back to Figure 7.13) with two reagents. 

Figure 9-6. Reaction scheme, for the internal reduction according to Figure 9-5.

Figure 9-12. a) Scheme of the internal solid state reaction CaO +Ti02 = CaTi03 in the matrix crystal NiO. Concentration profiles and precipitate are indicated, b) Photograph of cross section with internal reaction zone (T = 1340 C, t = 413 h reaction time). 

The reaction of DMAD with the cyanocarbalkoxy pyridinium methylide 39 in various solvents has also been studied.64 In benzene the expected indolizine 40 was obtained. In dimethylformamide, the car-bethoxy methylide gave some elimination of CN instead of COOR. However, in acetonitrile no indolizine was formed at all. The 1 1 crystalline adducts that were isolated were formulated on the basis of chemical and spectroscopic evidence as the highly stabilized ylids (41), formed by an internal rearrangement (Scheme 8). 

Acetylenic monomers also appeared to undergo polymerisation with conventional olefin metathesis catalysts. This relates to monosubstituted highly branched alkylacetylenes and arylacetylenes as well as disubstituted acetylenes (internal alkynes) [16-18], It has been demonstrated that acetylene itself may also be polymerised using olefin metathesis catalysts [19,20]. The polymerisation of alkynes [scheme (2)] involves a metathesis reaction [scheme (5) of Chapter 2] analogously to that of cycloolefins [21] ... 

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