Alkyl sulfones: discovery of novel structural types with differentiated opportunities for insect control.

The discovery of novel chemical classes with novel modes of action for insect control form the backbone of innovation with the goal to deliver much-needed solutions into the hands of growers. Over the last decade, alkyl sulfones have emerged as one of the most versatile new classes and are under intensive investigation in many R&D programs in the industry, with Sumitomo Chemicals recently introducing oxazosulfyl as a first active ingredient to the market. In this review, we discuss some of our strategies to invent novel classes based upon ligand-based design, and also show how incorporation of physical chemical properties into our design enabled us to predictably control chewing and sucking pests. © 2024 Society of Chemical Industry.

A general approach to the synthesis of enantiopure 19-nor-vitamin D3 and its C-2 phosphate analogs prepared from cyclohexadienyl sulfone.

A synthesis of enantiopure 19-nor-Vitamin D(3) and its C-2 substituted cyclic phosphate analogs is achieved via in situ trapping of an α-sulfonyl anion with a CD-ring allyl chloride and 1,2-eliminative desulfonylation exploiting the basic properties of TBAF. The A-ring is prepared via anti-selective dithiane addition to vinyl sulfone and LiBH(4) mediated sequential bis reduction of an epoxy vinyl sulfone.

Intramolecular methylation of an allyl sulfone via lithium alkoxyaluminate; application to the enantioselective synthesis of the CD ring of vitamin D3.

Alcohol-directed intramolecular methylation of an enantiopure allyl sulfone using AlMe(3) provides a trans-hydrindane CD ring alcohol. The substrate cis-CD ring allyl sulfone alcohol is prepared via intramolecular allyl sulfonyl anion addition to aldehyde using Ba(OH)(2).

Fluoride-mediated elimination of allyl sulfones: application to the synthesis of a 2,4-dimethyl-A-ring vitamin D3 analogue.

A coupling strategy for the synthesis of 2,4-dimethyl-1α,25(OH)(2)D(3) is achieved which involves methylation of a pro-A ring vinyl sulfone and in situ traping of the allyl sulfonyl anion with a CD ring allyl chloride. TBAF-promoted 1,2-eliminative desulfonylation and concomitant silyl ether deprotection gives the vitamin D(3) analogue.

S(N)2' addition/1,2-elimination of dimethylsulfonium methylide with epoxy vinyl sulfones: synthesis of exocyclic cross-conjugated dienyl sulfones.

Dimethylsulfonium methylide undergoes S(N)2' addition/1,2-elimination with epoxy vinyl sulfones to generate enantiopure six and seven membered cross-conjugated hydroxy vinyl sulfones. Moderate to excellent yields were obtained for both six and seven membered substrates.