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  • Polyphosphoric acid trimethylsilyl ester promoted intramolecular acylation of an olefin by a carboxylic acid: convenient construction of C-18-functionalized delta14-hecogenin acetate.

Polyphosphoric acid trimethylsilyl ester promoted intramolecular acylation of an olefin by a carboxylic acid: convenient construction of C-18-functionalized delta14-hecogenin acetate.

Organic letters (2003-10-24)
Wei Li, Philip L Fuchs
ABSTRACT

[reaction: see text]. Polyphosphoric acid trimethylsilyl ester (PPSE)-promoted intramolecular Friedel-Crafts reactions on a nonaromatic carboxylic acid system have been investigated. Studies led to the synthesis of C-18 functionalized steroidal compounds 5 and 9a-d with strict retention of the spiroketals. Isomerization of spiroketal 9e was studied.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Hexamethyldisiloxane, puriss., ≥98.5% (GC)
Sigma-Aldrich
Hexamethyldisiloxane, ≥98%
Sigma-Aldrich
Hexamethyldisiloxane, viscosity 0.65 cSt (25 °C)
Sigma-Aldrich
Hexamethyldisiloxane, NMR grade, ≥99.5%
Sigma-Aldrich
Polyphosphoric acid, reagent grade, 115% H3PO4 basis
Sigma-Aldrich
Polyphosphoric acid, ~105% H3PO4 basis