Conversion of Cyclic Vinyl Sulfones to Transposed Vinyl Phosphonates

Abstract

Functionalized cyclic vinyl sulfones were directly converted to the "polarity reversed" vinyl phosphonates through an efficient one pot procedure. Ozonolysis of these vinyl sulfones and vinyl phosphonates furnish complementary sets of termini-differentiated ester-aldehydes. This strategy has been applied for preparation of segments needed for the synthesis of Aplyronine A. The scope and limitations of this transformation were defined.

Citric acid mediated catalytic osmylation/oxidative cleavage of electron deficient olefins: a vinyl sulfone study

“…26 Compound 5 Entry 2 contains a trans stereodiad that was an aplyronine A intermediate. 5,37 The crude epimeric acyloin 6 was subjected to the Criegee oxidation without further purification to yield lactol 7. The aplyronine A strategy sought to employ cyclic vinyl sulfone stereotetrads as precursors to linear dipropionate segments.…”

“…Early aplyronine A intermediate 15,5,7 contains an enantiomerically pure epoxide and provides enantiopure acyloin 16 with the epoxide intact (Entry 6). Criegee oxidation next afforded terminidifferentiated epoxide cleavage product 17.…”

“…3 Oxidative cleavage of electronically deactivated and/or sterically hindered olefins has proven historically quite difficult. Griesbaum 4 and Fuchs 5 reported the first ozonolysis of vinyl triflates, vinyl nitriles, and vinyl sulfones, 1,2 respectively, in the 1990s. Ozonolysis of seven-membered vinyl sulfones was more extensively studied for the synthesis of polypropionate fragments of apoptolidin and aplyronine A.…”

Synthesis of Alkynyl Sulfones

“…Sulfones are valuable structures that have attracted the interest of synthetic chemists due to their ability to stabilize α‐carbanions, their strong electron‐withdrawing properties, and their chameleonic abilities . Alkynyl sulfones are sulfone derivatives that have shown very important synthetic applications, e. g., as dienes in cycloadditions, in the synthesis of disubstituted alkynes and in the alkynylation of diverse structures of biological interest, which can subsequently be functionalized (Figure ) . Owing to the importance of these materials, different methodologies for the synthesis of alkynyl sulfones have been reported over the years.…”

Recent Progress in The Synthetic Study of an Antitumor Marine Macrolide Aplyronine A and Related Molecules

“…The vinyl sulfone 5629 was converted into aldehyde 58 as the C15-C20 segment in four steps. The vinyl sulfone 5629 was converted into aldehyde 58 as the C15-C20 segment in four steps.…”