Allenes Lewis acid catalysed

New routes to camphenilone and dehydrocamphene derivatives using alkenes614 or allenic esters as dienophiles in Diels-Alder reactions515 have been developed. Lewis acid-catalysed coupling of a,0-unsaturated methyl ketones with cyclo-pentadiene favoured exo-products except when TiCl4 was used,516 and led to isocamphanes that were spasmolytics.517 The tricyclene (214) could be converted... 

Another way that allenes can be used to provide an acyl anion equivalent is by the Lewis acid catalysed addition of propargyl silanes to electrophiles 109 followed by oxidative cleavage of the allene. The intermediate vinyl cation 110 is stabilised by the silicon (3-effect (chapter 12) and loss of the Me3Si group gives the allene 111. Oxidative cleavage of the sensitive allene reveals that it has acted as a reagent for the formyl anion. 

A one-step Lewis acid-catalysed intermolecular 4- -3-cycloaddition of aromatic a,)3-unsaturated aldehyde and ketones (105) with epoxides (106) formed seven-membered oxacycles (107) under mild conditions (Scheme 34).The effect of oxygen-, sulfur-, and halogen-substituents on the reactivity of nitrogen-stabilized oxyallyl cations in 4- -3-cycloaddition reactions has been extensively investigated. Aza-oxyallyl cationic intermediates react with cyclopentadiene and furan via an aza-4 -I- 3-cycloaddition reaction to form bicyclic cycloadducts in moderate yields. The intramolecular formal 4- -4-cycloaddition of conjugated enynes with an e-deflcient cyclobutene (108) yielded a strained six-membered cyclic allene (109) that isomerized to a 1,3-cyclohexadiene (110). This intermediate underwent a thermal or acid-promoted six-electron electrocyclic ring opening to yield a 2,4,6-cyclooctatrienone (111) (Scheme 35). ... 

The Lewis-acid-promoted formal intramolecular 3 + 2-cycloaddition of cyclopropane 1,1-diesters with allenes (25) produced [4.3.0]nonanes (26) and [3.2.1]octanes (27) by parallel-cycloaddition and cross-cycloaddition, respectively (Scheme 8). Similarly, the Lewis-acid-catalysed formal intramolecular 3 + 2-cycloaddition reactions of cyclopropane 1,1-diesters with alkenes produced bridged[n.2.1]carbocyclic compounds with excellent stereo- and regio-selectivity under mild conditions. This reaction has been successfully applied to the total synthesis of tetracyclic diterpenoids phallocladanol and phallocladene. ... 

A rapid approach to a-sulphinyl-ketones is the Lewis-acid-catalysed sulphinyl-ation of trimethylsilyl enol ethers by sulphinyl chlorides. In the absence of the Lewis acid stannic chloride, yields of the sulphoxide were very low. Allenic sulphoxides are readily converted into the P-keto-sulphoxide via the intermediate enamine [equation (38)]. Allene sulphones also add allylic alcohols under basic... 

A general route to 6-substituted valerolactones (112) is by condensation between aldehydes and the dianion derived from butynoic acid followed by hydrogenation using Lindlar s catalyst.During the synthesis of some steroid derivatives, use has been made of an intramolecular Wadsworth-Emmonds procedure to construct an unsaturated valerolactone group (114) from phos-phonate (113) (c/. 3, 87). A new preparation of ( )-pestalotin (115) has as its pivotal step a Lewis acid-catalysed condensation between 2-benzyloxyhexanol and diketen. /3-Ethylenic valerolactones (116) can be obtained from the corresponding /3-allenic acids by treatment with methanolic boron trifluoride (c/. 3, 89). 

Anodic oxidation of N, N.-dimethylaniline in methanol yields the -methoxylated derivative (72), which reacts with substituted alkenes in the presence of Lewis acid to give a wide range of tetrahydroquinolines (e.g. 73).94- The adduct (75) from N-methylaniline and allene-1,3-dicarboxylic acid dimethyl ester (7 ) can be converted into the 4-quinolone (76) on treatment with polyphosphoric acid. 95 The use of nitrobenzenes as quinoline precursors is exemplified by the reaction sequence depicted in Scheme 17. The transition-metal-catalysed transformation is thought to involve the reduction of the nitrobenzene to the corresponding aniline via a nitrene intermediate.96... 

The nickel-iminophosphine-catalysed 4- -2-cycloaddition of enones with allenes formed highly substituted dihydropyrans. The enantioselective amine-catalysed 4-I-2-cycloaddition of allenoates with oxo-dienes produced polysubstituted dihydropyrans in high yields and with high enantioselectivities. Novel enam-ine/metal Lewis acid bifunctional catalysis has been used in the asymmetric inverse-electron-demand hetero-Diels—Alder reactions of cyclic ketones with Q ,j9-unsaturated a-ketoesters. The 4- -2-cycloaddition of acylketenes (80) with 2-unsubstituted and 2-monosubstituted 3-aryl-2//-azirines (81) produced 1 1 (82) or 2 1 (83) adducts, being derivatives of 5-oxa-l-azabicyclo[4.1.0]hept-3-ene or 5,7-dioxa-l-azabicyclo[4.4.1]undeca-3,8-diene. The formation of the monoadducts proceeds via a stepwise non-pericyclic mechanism (Scheme 25). A-heterocyclic carbene-catalysed 4- -2-cycloaddition of ketenes with 1-azadienes yielded optically active 3,4-dihydropyrimidin-2-ones (93% ee) ... 

Two separate studies on photocyclization of allenes include examples of how Lewis acids and the polarity of the solvent affect the regioselectivity of the addition of activated olefins and 1,1-dicyclopropylallene, and provide details of the intramolecular photoaddition of allenes to a,p-cyclohexenones. Copper(i) trifluoromethanesulphonate has been found to catalyse the intramolecular photocyclization of several monocyclic (3- and Y"(pent-4-enyl)allyl alcohols for instance, the allyl alcohol (19) forms the tricyclic hydrocarbon (20), which is an... 

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