Rhodium Mediated CH Bond Functionalisation Leading to Carboxylate Derivatives

Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species

“…Rearrangement of 2‐rhodaoxetanes to allyl‐β‐alkyl‐hydroxide species followed by β‐hydroxy elimination gives access to [(allyl–diene)Rh III OH] + species. To the best of our knowledge, this is the first unambiguous example of a concerted β ‐ hydroxy syn ‐elimination reaction at a rhodium center,16, 17 which adds further diversity to the remarkable palette of 2‐metallaoxetane reactivity 12. The active [(allyl)Rh III ‐polymeryl] + growing chains are formed by carbene insertion into the RhOH bond.…”

Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species

“…To the best of our knowledge, this is the first unambiguous example of a concerted bhydroxy syn-elimination reaction at a rhodium center, [16,17] which adds further diversity to the remarkable palette of 2metallaoxetane reactivity. These turn out to be cationic [(allyl)Rh III -polymeryl] + species.…”

“…Rearrangement of 2-rhodaoxetanes to allyl-b-alkyl-hydroxide species followed by b-hydroxy elimination gives access to [(allyl-diene)Rh III ÀOH] + species. To the best of our knowledge, this is the first unambiguous example of a concerted bhydroxy syn-elimination reaction at a rhodium center, [16,17] which adds further diversity to the remarkable palette of 2metallaoxetane reactivity. [12] The active [(allyl)Rh III -polymeryl] + growing chains are formed by carbene insertion into the Rh À OH bond.…”

Comparative study of the volatile composition in wines obtained from traditional vinification and from the Ganimede method

“…The complexes [M(O)(O 2 ) 2 (py)] (M=Cr, Mo; py=pyridine) react with electron‐rich enol ethers to yield the corresponding dioxetanes,8a but the products are formed by two consecutive mono‐oxygenation reactions and involve intermediate formation of the corresponding epoxides. Apart from mono‐oxygenation of 1,5‐cyclooctadiene,2c oxygenation of 1,5‐cyclooctadiene with [Rh(O 2 )(Cl)(PPh 3 ) 3 ], which can be prepared from dioxygen, produces 1,4‐cyclooctanedione 8b,c. However, this rare case of transition metal mediated alkene dioxygenation with O 2 is rather slow and is accompanied by competitive monooxygenation of the phosphine ligand.…”