Isoprene complexes

Spontaneous homopolymerization of the (isoprene-complexed acrylonitrile) complex ... 

While the unsubstituted butadiene complex does not react, the isoprene complex yields a 2 1 addition product 154 when trace amounts of Fe(CO)s are present 132, 133). 

Both 211 and 297 (see also Section II-C.2) have been foxmd to effect double C—H activation of cyclic ethers to afford Fischer-type carbene complexes (Section II-D.2), leading in some instances to C-C coupling reactions." Comparable double C-H activations have also been effected using 194," and the /" -isoprene complex Tp Ir(f/" -2-MeC4H5) (238) with several substrates (MeOPh, Me2NPh,... 

The rational synthesis of anionic, neutral, and cationic dinuclear palladium complexes containing bridging conjugated dienes is shown in Scheme 32 for butadiene, and consists of the formal redox condensation of Pd(0) and Pd(ii) complexes in the presence of the conjugated diene to give Pd(l) dimers. In addition, some complexes with isoprene and with 1,3-cyclohexadiene were made. The isoprene complexes consisted of the expected pair of regioisomers in the case of the less symmetric neutral molecules. The crystal structures of one neutral complex... 

Cholesterol was isolated m the eighteenth century but its structure is so complex that Its correct constitution was not determined until 1932 and its stereochemistry not verified until 1955 Steroids are characterized by the tetracyclic ring system shown m Figure 26 9a As shown m Figure 26 9b cholesterol contains this tetracyclic skeleton modified to include an alcohol function at C 3 a double bond at C 5 methyl groups at C 10 and C 13 and a C Hn side chain at C 17 Isoprene units may be discerned m var lous portions of the cholesterol molecule but the overall correspondence with the iso prene rule is far from perfect Indeed cholesterol has only 27 carbon atoms three too few for It to be classed as a tnterpene... 

The dimerization of isoprene has been accompHshed by methods other than heating. Thus isoprene has been dimerized by uv radiation in the presence of photosensitizers to give a complex mixture of cyclobutane, cyclohexene, and cyclooctadiene derivatives (36,37). Sulfuric acid reportedly... 

Other Compounds. Primary and secondary amines add 1,4- to isoprene (75). For example, dimetbylamine in ben2ene reacts with isoprene in the presence of sodium or potassium to form dimetby1(3-metby1-2-buteny1)amine. Similar results are obtained with diethylamine, pyrroHdine, and piperidine. Under the same conditions, aniline and /V-metbylaniline do not react. Isoprene reacts with phenol in the presence of aluminum phenoxide (76) or concentrated phosphoric acid (77) to give complex products. 

Another group of isoprene polymerization catalysts is based on alanes and TiCl. In place of alkyl aluminum, derivatives of AlH (alanes) are used and react with TiCl to produce an active catalyst for the polymerization of isoprene. These systems are unique because no organometaHic compound is involved in producing the active species from TiCl. The substituted alanes are generally complexed with donor molecules of the Lewis base type, and they are Hquids or soHds that are soluble in aromatic solvents. The performance of catalysts prepared from AlHCl20(C2H )2 with TiCl has been reported (101). 

Terpenes are characterized as being made up of units of isoprene in a head-to-tail orientation. This isoprene concept, invented to aid in the stmcture deterrnination of terpenes found in natural products, was especially useful for elucidation of stmctures of more complex sesquiterpenes, diterpenes, and polyterpenes. The hydrocarbon, myrcene, and the terpene alcohol, a-terpineol, can be considered as being made up of two isoprene units in such a head-to-tail orientation (1). 

Sesquiterpenes are formed by the head-to-tad arrangement of three isoprene units (15 carbon atoms) there are, however, many exceptions to the rule. Because of the complexity and diversity of the substances produced in nature, it is not surprising that there are many examples of skeletal rearrangements, migrations of methyl groups, and even loss of carbon atoms to produce norsesquiterpenoids. 

A living cationic polymeriza tion of isobutylene and copolymeriza tion of isobutylene and isoprene has been demonstrated (22,23). Living copolymerizations, which proceed in the absence of chain transfer and termination reactions, yield the random copolymer with narrow mol wt distribution and well-defined stmcture, and possibly at a higher polymerization temperature than the current commercial process. The isobutylene—isoprene copolymers are prepared by using cumyl acetate BCl complex in CH Cl or CH2CI2 at —30 C. The copolymer contains 1 8 mol % trans 1,4-isoprene... 

Halogenated Butyl Rubber. The halogenation is carried out in hydrocarbon solution using elemental chlorine or bromine in a 1 1 molar ratio with enchained isoprene. The reactions ate fast chlorination is faster. Both chlorinated and brominated butyl mbbers can be produced in the same plant in blocked operation. However, there are some differences in equipment and reaction conditions. A longer reaction time is requited for hromination. Separate faciUties are needed to store and meter individual halogens to the reactor. Additional faciUties are requited because of the complexity of stabilising brominated butyl mbber. 

The mid-block monomers are primarily isoprene and butadiene. These diolefins can polymerize in several ways. The isomeric structure of the final polymer has a strong impact on its properties and thermal stability. Isomeric composition is easily varied by changing the polymerization solvent or adding complexing agents. The typical isomeric structures for isoprene and butadiene mid-blocks are shown in Fig. 2. 

Poly(butadiene-l>-vinyl pyridine) or poly(isoprene-l>-vinyl pyridine) Ni/Et3Al catalysis BF3 and CFAlEt used to complex vinyl pyridine to increase rate of hydrogenation BFj released by NH4OH... 

The irradiation of 2,5-dimethylfuran in the presence of mercury vapor gave a complex mixture of products. Carbon monoxide and propene were removed as gaseous products. Then, cis- and rran.s-l,3-pentadiene, isoprene, 1,3-dimethylcyclopropene, 2-pentyne, 2-ethyl-5-methylfuran, hexa-3,4-dien-2-one, 1-methyl-3-acetylcyclopropene, and 4-methylcyclopent-2-enone were obtained (Scheme 8) (68JA2720 70JA1824). The most abundantproduct was the cyclopentenone 19, the second was the 1,3-pentadiene 12, while the third product was the cyclopropenyl derivative 18. 

The interest in chiral titanium(IV) complexes as catalysts for reactions of carbonyl compounds has, e.g., been the application of BINOL-titanium(IV) complexes for ene reactions [8, 19]. In the field of catalytic enantioselective cycloaddition reactions, methyl glyoxylate 4b reacts with isoprene 5b catalyzed by BINOL-TiX2 20 to give the cycloaddition product 6c and the ene product 7b in 1 4 ratio enantio-selectivity is excellent - 97% ee for the cycloaddition product (Scheme 4.19) [28]. 

Regardless of Llieu apparent structural differences, all terpenoids are related. According to a formalism called the isoprene rule, they can be thought of as arising from head-to-tail joining of 5-carbon isoprene units (2-methyl-1,3-butadiene). Carbon 1 is the head of the isoprene unit, and carbon 4 is the tail. For example, myreene contains two isoprene units joined head to tail, forming an 8-carbon chain with two 1-carbon branches. a-Pinene similarly contains two isoprene units assembled into a more complex cyclic structure, and humulene contains three isoprene units. See if you can identify the isoprene units in a -pinene and humulene. 

Isoprene itself is not the true biological precursor of terpenoids. As we ll see in Chapter 27, nature instead uses two "isoprene equivalents"—isopentenvl diphosphate and dimethylallyl diphosphate—which are themselves made by two different routes depending on the organism. Lanosterol, in particular, is biosynthesized from acetic acid by a complex pathway that has been worked out in great detail. 

Inhibition of olefin polymerization occurred when its basicity was not sufficient to produce an appreciable displacement of initiator from the aldehyde-acid complex isoprene, cyclopentadiene and styrene were in this category. 

It has been established that alkoxy alkenylcarbene complexes participate as dienophiles in Diels-Alder reactions not only with higher rates but also with better regio- and stereoselectivities than the corresponding esters [95]. This is clearly illustrated in Scheme 51 for the reactions of an unsubstituted vinyl complex with isoprene. This complex reacts to completion at 25 °C in 3 h whereas the cycloaddition reaction of methyl acrylate with isoprene requires 7 months at the same temperature. The rate enhancement observed for this complex is comparable to that for the corresponding aluminium chloride-catalysed reactions of methyl acrylate and isoprene (Scheme 51). 

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