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A synthetic approach toward nitiol: Construction of two 1,22-dihydroxynitianes

TitleA synthetic approach toward nitiol: Construction of two 1,22-dihydroxynitianes
Publication TypeJournal Article
Year of Publication2006
AuthorsWilson, MS, Woo, JCS, Dake, GR
JournalJournal of Organic Chemistry
Volume71
Pagination4237-4245
Date PublishedMay
Type of ArticleReview
ISBN Number0022-3263
Keywords1ST TOTAL-SYNTHESIS, ACTIVE, ALKYL BROMIDES, ARYL GRIGNARD-REAGENTS, BETA-SILOXY ALDEHYDES, CARBON BOND FORMATION, IRELAND-CLAISEN REARRANGEMENT, PAUSON-KHAND REACTION, PLAGIOSPIROLIDE-A, TRANSITION-METAL CATALYSIS, ZIRCONIUM-CATALYZED CARBOALUMINATION
Abstract

Synthetic work toward the total synthesis of nitiol has culminated in the construction of two epimeric hydroxylated derivatives, the 1,22-dihydroxynitianes. Key stereodefining steps in the construction of the A-ring fragment (13) were the use of a siloxy-epoxide rearrangement reaction, a Pauson-Khand reaction, a Norrish 1 photochemical cleavage reaction, and a highly regio- and stereoselective hydrostannylation reaction of an ynoate. The stereochemistry of the synthetically challenging C-ring fragment (20) was established using an Ireland-Claisen reaction and a Grubbs ring-closing metathesis process as key steps. The 12-membered B-ring of the nitiane skeleton was constructed using a copper-promoted Stille cross-coupling and a Kishi-Hiyama-Nozaki carbonyl addition reaction. Unfortunately, the carbonyl addition reaction produced hydroxyl functionality that could not be selectively removed. Consequently, a synthesis of epimeric 1,22-dihydroxynitianes, which are compounds that are structural hybrids of two natural products, nitiol and variculanol, was completed.

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