23897-15-6Relevant articles and documents
Halpern,Mislow
, p. 5224 (1967)
An Interrupted Pummerer/Nickel-Catalysed Cross-Coupling Sequence
Aukland, Miles H.,Talbot, Fabien J. T.,Fernández-Salas, José A.,Ball, Matthew,Pulis, Alexander P.,Procter, David J.
supporting information, p. 9785 - 9789 (2018/07/31)
An interrupted Pummerer/nickel-catalysed cross-coupling strategy has been developed and used in the elaboration of styrenes. The operationally simple method can be carried out as a one-pot process, involves the direct formation of stable alkenyl sulfonium salt intermediates, utilises a commercially available sulfoxide, catalyst, and ligand, operates at ambient temperature, accommodates sp-, sp2-, and sp3-hybridised organozinc coupling partners, and delivers functionalised styrene products in high yields over two steps. An interrupted Pummerer/cyclisation approach has also been used to access carbo- and heterocyclic alkenyl sulfonium salts for cross-coupling.
Stoichiometric reduction of CO2 to CO by phosphine/AlX 3-based frustrated Lewis pairs
Menard, Gabriel,Gilbert, Thomas M.,Hatnean, Jillian A.,Kraft, Anne,Krossing, Ingo,Stephan, Douglas W.
supporting information, p. 4416 - 4422 (2013/09/02)
The reactions of the bulky phosphines Mes3P or (otol) 3P with AlX3 (X = I, Br, Cl) and CO2 are probed and shown to give complexes of the form Mes3PC(OAlX 3)2 (X = I (3), Br (4), Cl (5)) and (otol) 3PC(OAlI3)2 (6). The former compounds under CO2 are further transformed to Mes3PC(OAlX 2)2OAlX3 (X = I (8), Br (10)) and [Mes 3PX][AlX4] (X = I (9), Br (11)). These latter reactions are thought to proceed via dissociation of alane, as evidenced by the generation of (otol)3PC(OAl(C6F5)3) from (otol)3PC(OAl(C6F5)3)2 (7) and the isolation of (otol)3PC(O)OAl(OC(CF3) 3)3 (15). Subsequent insertion of CO2 into the Al-X bond is evidenced by the characterization of [(C6F 5)C(O)OAl(C6F5)2]2 (14) from the reaction of Al(C6F5)3 and CO 2. The isolation of Al(C6F5) 3·2(C6H5Br) (16) also suggests dissociation of Al(C6F5)3 from 7 may be facilitated by interactions with solvent. Kinetics of the formation of 8/9 from 3 show the reaction is first order in 3 and CO2 and the rate-determining step involves an associative process. A mechanism involving dissociation of alane and subsequent insertion of CO2 into the Al-X bond is proposed.
