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6.4.1.1 Total Synthesis of Sarcophytol A The rst total synthesis of sarcophytol A (3), which was reported by Takayanagi et al. in 1990,80,81 was achieved in a highly stereo- and enantioselective manner starting from E,E-farnesol (91); it included (1) a newly developed Z-selective (Z : E ! 35 : 1) Horner Emmons reaction with a phosphonate nitrile, (2) modi ed cyanohydrin macrocyclization, and (3) enantioselective (93% ee) reduction of macrocyclic ketone 100 as its key steps (Scheme 6-1). Enantiomerically pure sarcophytol A (3) was obtained by a single recrystallization. An improved synthetic process appropriate for a large-scale preparation with geraniol as the starting material was also developed. It included a new ketal Claisen rearrangement with 2,2-dimethoxy-2,3-dimethylbatan-2-ol for a-ketol isoprene elongation, which was applied to the sequence for highly stereoselective (E : Z ! 99 : 1) synthesis of trisubstituted g, d-unsaturated aldehydes, and acids (Scheme 6-2).82 c# create pdf417 Packages matching PDF417 - NuGet Gallery
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