Stereoselective Heck-Matsuda Arylations of Chiral Dihydrofurans with Arenediazonium Tetrafluoroborates; An Efficient Enantioselective Total Synthesis of (-)-Isoaltholactone

Abstract

The Heck-Matsuda arylation of chiral 2-(S)-hydroxy­methyl dihydrofurans (endocyclic enolethers) and its derivatives, employing arenediazonium tetrafluoroborates, was developed into a highly efficient, practical and diastereoselective synthetic process. This methodology was applied to the total synthesis of the styryllactone (-)-isoaltholactone in seven steps with an overall yield of ˜25%, from the readily available chiral 2-hydroxymethyldihydrofuran. The strategy permits the synthesis of several other aromatic analogues of isoaltholactone.

Key words

Heck reaction - palladium - diazonium compounds - catalysis - stereoselectivity

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9

The endocyclic enolether 12 is a rather volatile compound. Use of reduced pressure should be avoided during its isolation and purification.

10

An interesting alternative to the use of dihydrofuran is the use of a balloon of carbon monoxide. A dark blue solution forms after a few minutes of exposure which stays stable for a long time, without any signs of Pd precipitation. However, upon addition of the remaining reagents, formation of Pd black begins to occur in the reaction medium.