SmI2 mediated reductive addition of bis-phenylsulfones to ketones

The Julia Reaction

“…The authors initially used lithium naphthalenide as the reducing agent to cleave the CaS bond and generate the a-sulfonyl carbanion [55]. Subsequently, they improved their methodology by employing samarium diiodide instead of lithium naphthalenide [56] (Scheme 3.14).…”

“…Even the use of sulfoxides proved to be of no avail [52,53]. It is thus even more remarkable that the method reported by Falck and Mioskowsky affords tetrasubstituted b-hydro-sulfones in excellent yields [56]. It is quite possible that the unique properties of the Sm III salt, which acts as a Reaction 3.14 Scheme 3.14.…”

ChemInform Abstract: Synthesis of Unsaturated Nine‐Membered Ring Ethers (Δ3‐Oxonenes) Containing a Z‐ or E‐Configurated Double Bond: Thermodynamic versus Kinetic Control in Palladium‐Catalyzed Allylic Cyclizations.

“…In contrast, reductive monodesulfonylation with SmI 2 provided sulfone 8. [12] Subsequent oxidative desulfonylation [13] afforded the ketone 9 as a functionalized intermediate, well endowed for further synthetic manoeuvres (Scheme 5). The epoxyether alkynol 2 is readily accessible from inexpensive starting materials and serves as a key intermediate for preparing E-and Z-configurated cyclization precursors.…”

The Development of a Stereoselective Method for the Synthesis of Tetrasubstituted Derivatives of α,β‐Unsaturated Carboxylic Acids

“…Other synthetic methods are therefore more applicable for the preparation of multisubstituted alkenes. These include the coupling of substituted vinyl halides or pseudo ‐halides with organometallic compounds , elimination reaction , carbometallation of alkynes , and carbonyl olefination .…”