1,3-diene utility

An excellent, general procedure for the stereoselective synthesis of conjugated 13,13 dienes utilizes 1-halo-l-alkynes and thexylborane (36). We prepared the compound XXXX (which is the 13,13 isomer of the Lobesia botrana pheromone XXIX) in >98% stereochemical purity by this procedure (Figure 19). 

This chemistry was extended to a number of bicyclic alkenes and dienes utilizing various chelating axially chiral bisphosphine iridium catalysts (Scheme 11.5) [29]. Further synthetic transformations of the chiral hydroamination product 13 provide access to functionally substituted chiral cyclopentylamines with multiple stereocenters, such as 14 and IS. It should be noted that alkylamines, such as octylamine or N methyl aniline, and sterically encumbered aniline derivatives, such as 0 toluidine or o anisidine did not undergo hydroamination reactions under these conditions. 

Chiral precursors have been also used for the preparation of enantiopiu-e dienes utilized in the construction of an AB segment [175] and a tetracyclic moiety [176] of the anthracyclinones. 

Diels-Alder cycloadditons have been explored on solid supports, and Winkler and Kwak have demonstrated a chemoselective variant that affords a single reaction of a dienophile containing two reactive double bonds with a bis-diene. Utilizing bis-reactive Diels-Alder reagents in the absence of a solid support is problematic as competing oligomerization can occur. Thus, a dienophile was immobilized as 8 and reacted with the... 

Diene carboxylates can be prepared by the reaction of alkenyl halides with acrylates[34]. For example, pellitorine (30) is prepared by the reaction of I-heptenyl iodide (29) with an acrylate[35]. Enol triflates are reactive pseudo-halides derived from carbonyl compounds, and are utilized extensively for novel transformations. The 3,5-dien-3-ol triflate 31 derived from a 4,5-unsaturated 3-keto steroid is converted into the triene 32 by the reaction of methyl acrylate[36]. 

Cyclopropanes can also be obtained by the reaction of vinyltrialkylborates with aldehydes followed by treatment with phosphoms pentachloride and base (300), and by the rearrangement of 5-substituted alkynyltrialkylborates (308). It is also possible to utilize this approach for the synthesis of five- and six-membered rings (3). Trans-1,4-elimination ia cycHc systems leads to the formation of stereodefined acycHc 1,5-dienes or medium-ring dienes, depending on the starting compound (309). 

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). 

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

Like HIIR, EPR has a fiiUy saturated backbone and has only unsaturation points available for vulcanization cross-linking in very small percentages of the pendent diene modifier (EPDM). It is an excellent aging compound with high dex fatigue life even when heavily loaded with fillers and is utilized in PCT white sidewalls. 

In the indazole series an example of a type (c) reaction (Figure 25) has been described utilizing a 1,3-dipole instead of a diene (Scheme 32) (76H(4)1655). The cycloadduct (351) is transformed into the triazole (352) on reaction with hydrochloric acid. 

Isolated tetrasubstituted double bonds do not react under these conditions and the saturation of trisubstituted double bonds is extremely slow, thus limiting the general utility of the method. This difference in reactivity is used to advantage for the selective deuteration of the -double bond in androsta-l,4-diene-3,17-dione (138). In homogeneous solution, saturation usually occurs from the a-side and consequently the deuterium labels are in... 

The ready reduction of iodohydrins is utilized in the Cornforth reaction for preparing olefins from epoxides. Here the opening and reduction are carried out in one step by treatment of the epoxide, in an acetic acid-sodium acetate buffer, with sodium iodide and zinc. A less common use of iodohy-drin reduction is illustrated in the synthesis of the diene (127) ... 

Syntheses of equilin have utilized deconjugation to introduce the A -double bond. The enol acetate-borohydride method gives the A -diene-3-ol (174). 

A -Dien-3-ol esters e.g., acetates) have greater utility as reaction intermediates than as protecting groups. They are prepared from A" -3-ketones by reaction with the acetic anhydride"" or by exchange with isopropenyl acetate. 

The Boekelheide reaction has found utility in other synthetic methodology. An approach to 2,3-pyridynes made use of this chemistry in the preparation of the key intermediate 30. Treatment of 28 with acetic anhydride produced the desired pyridone 29. Lithiation was followed by trapping with trimethylsilyl chloride and exposure to triflic anhydride gave the pyridyne precursor 30. Fluoride initiated the cascade of reactions that resulted in the formation of 2,3-pyridyne 31 that could be trapped with appropriate dienes in Diels-Alder reactions. 

Conjugated dienes can be epoxidized to provide vinylepoxides. Cyclic substrates react with Katsuki s catalyst to give vinylepoxides with high ees and moderate yields [17], whereas Jacobsen s catalyst gives good yields but moderate enantiose-lectivities [18]. Acyclic substrates were found to isomerize upon epoxidation (Z, )-conjugated dienes reacted selectively at the (Z)-alkene to give trans-vinylepoxides (Scheme 9.4a) [19]. This feature was utilized in the formal synthesis of leuko-triene A4 methyl ester (Scheme 9.4b) [19]. 

Block and Aslam441 reported a novel variant of the Ramberg-Backlund reaction in which a,/J-unsaturated a -bromoalkyl sulfones 368 afforded 1,3-dienes upon treatment with base. Since a -bromoalkyl sulfones 368 can be obtained readily by the initial treatment of olefins with bromomethanesulfonyl bromide under photoirradiation and subsequent treatment with triethylamine, this reaction was utilized for preparation of dienes which contain one additional carbon over that of the corresponding olefin. Starting from the cyclic olefins 369-372 the 1,3-dienes 373-376 were obtained442. 

The recent upsurge of interest in systems of theoretical interest demands practical syntheses of several important compounds. These are BICYCLO[2.l.0]PENT-2-ENE, BENZOCYCLOPROPENE, 1,6-OXIDO[10]ANNULENE, and others. ewdo-TRICYCLO[4.4.0.02 5]-DECA-3,8-DIENE-7,10-DIONE is utilized as a model for the use of CYCLOBUTADIENE IN SYNTHESIS, and a stable monomeric ketene, icri-BUTYLCYANOKETENE offers opportunities for further studies of this interesting species. 

Other commercially relevant monomers have also been modeled in this study, including acrylates, styrene, and vinyl chloride.55 Symmetrical a,dienes substituted with the appropriate pendant functional group are polymerized via ADMET and utilized to model ethylene-styrene, ethylene-vinyl chloride, and ethylene-methyl acrylate copolymers. Since these models have perfect microstructure repeat units, they are a useful tool to study the effects of the functionality on the physical properties of these industrially important materials. The polymers produced have molecular weights in the range of 20,000-60,000, well within the range necessary to possess similar properties to commercial high-molecular-weight material. 

Diels-Alder reaction is one of the most fundamental reactions for organic synthesis. Its synthetic utility is unquestioned. The stereochemistry of the reactions has attracted much attention. The retention of stereochemistry in the diene and the dienophile, the predominant formation of endo-attack products in the reactions of cyclic dienes, and highly controlled regioselectivity in the reactions of substimted dienes and... 

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