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By G. Pattenden

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Application to the enantiospecific synthesis of chiral cyclopentenols, however, is limited by the availability of appropriately substituted chiral substrates. e. 82 The chiral ( 2 ) allyl ethers (63)78 and (64)79 serve as useful precursors of an alarm pheromone (65) of the leaf-cutting ant (Atta texana) and 1 ephedrine (66), respectively, both sequences exhibiting high enantio- and erythro-selectivity (Scheme 46). 80 Finally, the asymmetric [2,3] Wittig rearrangement shown in Scheme 47 involving a chiral enolate as the migrating terminus is clearly and important development of this methodology.

5-3:l. Luengo and Koreeda have developed a highly stereoselective synthesis of both ( & ) - and (Z)-l-alkoxybuta-Il3-dienes which proceeds the syn- and anti-dehydrative decarboxylation of the readily separable erythro- and threo-hydroxy-acids (119) and (1201, respectively (Scheme 8 7 ) . 13* A facile route to the synthetically useful I-phosphoryl- and l-sulphonyl-1,3-dienes has been reported. 137 Dienes of this type, bearing chiral auxilliaries, are of particular interest since they may offer useful diastereofacial selectivity on reaction with dienophiles.

Reagents: i. m ) z C u L i ; ii, LDA Scheme 60 0 (82) Reagents: i, Pr'MgCI, C u l ; ii, LDA Scheme 61 SPh But Me,Si 6 OMe Rv ... 111, iv t & + -s R p h ' 0 Rcogcnts: i, SiOz, hexanc, A ; ii. 30% H2SO4 ; iii. CrOg , H#Q, Schema 62 OH acetone; iv, DBU General and Synthetic Methods 36 Br Bu0 Reagents: i, ButgSnH, AIBN; ii, Jones oxidation Scheme 63 . Reagents: i, 2 BusLi; ii, . ; iii, H + , A Scheme 64 j i, ii PhSOZ H ‘IY7fiNx PhS@ Reagents: i, 2 BuLi; ii, C8H17CHO; iii, H+ Scheme 65 H Ph 1: Saturated and Unsaturated Hydrocarbons 37 4-alkylsilylfurans (9.

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