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Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249
Graphical Abstract
Figure 1: CD-based mono- and diphosphines with inward-pointing phosphorus atoms.
Scheme 1: Complexation of a "PdCl(dmba)" unit by HUGPHOS ligands.
Scheme 2: Reaction of HUGPHOS-1 with [MCl2(PhCN)2] complexes (M = Pd, Pt). Only one isomer with a given MeO–M...
Scheme 3: Synthesis of complexes 3–5.
Figure 2: X-ray structure of aqua palladium complex 5 [44] (top: side view; bottom: view from the primary face). ...
Scheme 4: Dehydration of Pd(II) complex 5.
Figure 3: Ruthenium complexes 7 and 8 in Newman projection along the Ru–P bond.
Figure 4: Titration of HUGPHOS-1 with [Rh(CO)2Cl]2 at 25 °C.
Scheme 5: Synthesis of rhodium carbonyl complexes 9–11.
Scheme 6: Synthesis of rhodium complexes 12 and 13.
Scheme 7: Selective formation of complex 14 under 40 bar CO/H2 at 80 °C.
Figure 5: High pressure NMR spectra of 13 under CO/H2 (1:1) recorded in toluene-d8 (at various temperatures a...
Figure 6: IR spectra of 14 recorded in CH2Cl2 at 50 °C under 40 bar of CO/H2 1:1.
Figure 7: Calculated structures (Spartan 10) of trigonal bipyramidal [RhH(CO)3(HUGPHOS-2)] with the phosphoru...
Scheme 8: Possible mechanism for the hydroformylation of styrene when using monophosphine complexes 12 or 13 ...
Scheme 9: Simplified Heck coupling mechanism when using HUGPHOS-1 or HUGPHOS-2 as ligands. Doted lines stand ...