84612-77-1Relevant articles and documents
Gold Complexes with ADAP Ligands: Effect of Bulkiness in Catalytic Carbene Transfer Reactions (ADAP = Alkoxydiaminophosphine)
Fructos, Manuel R.,Molina, Francisco,Pérez, Pedro J.,Pizarro, Juan Diego
supporting information, (2020/07/14)
A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been synthetized through a one-pot simple protocol in which the ADAP ligand is prepared in situ before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect superior to those of phosphine or phosphite ligands. Evaluation of the buried volume (percentVBur) indicates a steric hindrance higher than those of several NHC, PR3, and P(OR3) ligands, in the context of AuCl(L) complexes. These complexes promote the catalytic transfer of a carbene group from ethyl diazoacetate to alkenes and alkanes. In the case of styrene, both the Csp2-H bonds and the Ca? C bond are functionalized, the relative ratio depending on the catalyst employed and correlating well with the percentVBur value. Data available allow proposing that these compounds display quite similar electronic properties but differ in steric properties, a variable that can be readily controlled upon modifying the alkoxy group at the ADAP ligand by simply replacing the starting alcohol employed in the synthesis.
Water as the Reaction Medium for Intermolecular C-H Alkane Functionalization in Micellar Catalysis
álvarez, María,Gava, Riccardo,Rodríguez, Manuel R.,Rull, Silvia G.,Pérez, Pedro J.
, p. 3707 - 3711 (2017/06/09)
A series of alkanes CnH2n+2 have been functionalized in water as the reaction medium, using a silver-based catalyst, upon the insertion of carbene (CHCO2Et from N2CHCO2Et) groups into the carbon-hydrogen bonds of hexane, cyclohexane, or 2-methylbutane, among others. The regioselectivity toward the distinct reaction sites is identical to that found in neat alkane, the water-based system allowing the use of a much shorter excess of the hydrocarbon. This is the first example of the intermolecular functionalization of alkanes with this strategy in water. The functionalized alkanes partially undergo the incorporation of a second carbene unit to provide α-(acyloxy)acetates, in an unprecedented tandem reaction of this nature.
Functionalization of non-activated C-H bonds of alkanes: An effective and recyclable catalytic system based on fluorinated silver catalysts and solvents
Fuentes, M. Angeles,Munoz, Bianca K.,Jacob, Kane,Vendier, Laure,Caballero, Ana,Etienne, Michel,Perez, Pedro J.
supporting information, p. 1327 - 1334 (2013/03/14)
The complexes Fn-Tp 4Bo,3R fAg(L) (Fn-Tp 4Bo,3R f=a perfluorinated hydrotris(indazolyl) borate ligand; L=acetone or tetrahydrofuran) efficiently catalyze the functionalization of non-activated alkanes such as hexane, 2,3-dimethylbutane, or 2-methylpentane by insertion of CHCO 2Et units (from N2CHCO2Et, ethyl diazoacetate, EDA) into their C-H bonds. The reactions are quantitative (EDA-based), with no byproducts derived from diazo coupling being formed. In the case of hexane, the functionalization of the methyl C-H bonds has been achieved with the highest regioselectivity known to date with this diazo compound. This catalytic system also operates under biphasic conditions by using fluorous solvents such as Fomblin or perfluorophenanthrene. Several cycles of catalyst recovery and reuse have been performed, with identical chemo- and regioselectivities. Copyright
