Acetals, functionalized dienes

An ingenious new method for the preparation of Woodward s intermediate (97) by Pearlman70 constitutes another formal synthesis of reserpine. The essence of this new approach is an adaptation of the de Mayo reaction which allows the introduction of vicinal aldehyde and acetic ester functions on to a double-bond (Scheme 13). An internal [2tt + 27r] photocyclization of the diene (98) gave the tetracyclic cyclobutane derivative (99), which was converted into the ester (100) by standard procedures. Methanolysis of the acetate function with concomitant retro-aldol fission completed the introduction of the vicinal aldehyde and acetic ester functions obvious manipulation then gave the desired intermediate (97). 

The double bond of maleimides in very reactive towards electron-rich dienes, to give a normal Diels-Alder cycloaddition. Thus BMIs were used to obtain linear polyimides by reaction with several kind of dienes [46-51]. However the dienes are often difficult to prepare [51] and functionalized dienes have been used. Furan terminated oligomers react with BMIs at 70 °C leading to an oxygen-containing cycloadduct [52-57] which can react with acetic anhydride to give an aromatic imide (Fig. 13) [58-59]. 

Furthermore, this regio- and stereoselective bond formation between unsaturated carbon atoms was applied to the synthesis of functionalized dienes under extremely mild conditions. Thus, even vinylic boronic esters containing an allylic acetal moiety and alkenylboronate having a chiral protected allylic alcohol were successfully accomplished with vinylic iodides under aqueous conditions in 60-90% yield [30]. In addition, an exceptionally simple and efficient synthesis of a prostaglandin (PGEj) precursor was reported by Johnson, applying a DMF/THF/ water solvent mixture with a bis(diphenylphosphino)ferrocene palladium catalyst [31]. It is curious that the presence of water is an absolute necessity in order to succeed in this approach (Scheme 3). 

Cyclic exo-methylene compounds bearing a chiral acetal function prove to be excellent dieno-philes in the noncatalyzed Diels-Alder reaction. Dioxolanones 8 react with cyclopentadiene (9) and acyclic dienes 12 and 15 to afford adducts with diastereoselectivities as high as 100% 28,29. The major adduct 16 from the addition of 8b to diene 15 has been applied to the synthesis of the top half of kijanolide30. 

Heck-type reactions with enol carboxylates (e.g., vinyl acetate) are generally complex. Most common are reactions in which vinyl acetate is employed as an ethylene equivalent (see Scheme 24). However, an example of a preparatively useful reaction with an intact acetate function is given in entry 44.The reaction of vinyl triflates with vinyl phosphonates affords the corresponding conjugate dienylphosphonates (entry 45).f A new access to reactive nonaflates via a one-pot nonaflation-Heck reaction was recently reported (entry 46). " This reaction sequence starts from silyl enol ethers and provides functionalized 1,3-dienes in a simple manner, lodonium salts can be used as RPd precursors (entry 47). It is notable that the palladium(O) insertion preferentially occurs inbetween the iodonium ion and the vinylic, rather than the arylic sp -hybridized carbon (entry 47). Some years ago, Jeffery used acetylenic halides to achieve (JiJ-enynoates and (Ji)-enynones in fair yields at room temperature (entry 48). ... 

Functionalized dienes (ketene acetal/enol ether)... 

Monomers with multiple ether functionalities have also been polymerized via ADMET [76, 77]. Acetal-containing dienes have undergone ADMET polymerization with Grubbs [Ru] 1 catalyst to yield the polymer in quantitative yield [78,53]. Additionally, dienes containing primary, secondary, and tertiary alcohols have been shown to be amenable to ADMET polymerization (Figure 13.7) [79]. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

For the construction of oxygen-functionalized Diels-Alder products, Narasaka and coworkers employed the 3-borylpropenoic acid derivative in place of 3-(3-acet-oxypropenoyl)oxazolidinone, which is a poor dienophile in the chiral titanium-catalyzed reaction (Scheme 1.55, Table 1.24). 3-(3-Borylpropenoyl)oxazolidinones react smoothly with acyclic dienes to give the cycloadducts in high optical purity [43]. The boryl group was converted to an hydroxyl group stereospecifically by oxidation, and the alcohol obtained was used as the key intermediate in a total synthesis of (-i-)-paniculide A [44] (Scheme 1.56). 

By designing the repeat unit into the parent diene (containing either an alkyl branch or functionality), only a single type of repeat unit is formed upon polymerization, giving pure polymer microstructures. To date, perfectly controlled ADMET ethylene copolymers have included ethylene-CO,34 ethylene-vinyl alcohol,35 ethylene-vinyl acetate,36 and ethylene-propylene.20 Figure 8.12... 

Chemical pretreatments with amines, silanes, or addition of dispersants improve physical disaggregation of CNTs and help in better dispersion of the same in rubber matrices. Natural rubber (NR), ethylene-propylene-diene-methylene rubber, butyl rubber, EVA, etc. have been used as the rubber matrices so far. The resultant nanocomposites exhibit superiority in mechanical, thermal, flame retardancy, and processibility. George et al. [26] studied the effect of functionalized and unfunctionalized MWNT on various properties of high vinyl acetate (50 wt%) containing EVA-MWNT composites. Figure 4.5 displays the TEM image of functionalized nanombe-reinforced EVA nanocomposite. 

Trost and coworkers have devised a stereocontrolled 1,3-diene synthesis employing a palladium-catalysed decarboxylative elimination procedure from allylic acetates carrying carboxylic acid functionality ji- to the acetate group (equation 18)48. This decarboxylative elimination strategy has been applied to the synthesis of an insect pheromone, codlemone48a and the ethyl ester of vitamin A carboxylic acid (Table 5)48b. 

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