A Synthetic Approach toward Nitiol:  Construction of Two 1,22-Dihydroxynitianes

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−Khan...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2006-05, Vol.71 (11), p.4237-4245
Main Authors: Wilson, Michael S, Woo, Jacqueline C. S, Dake, Gregory R
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Gentianella - chemistry
Molecular Structure
Organic chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
Terpenes - chemical synthesis
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0604585