Bismuth‐Catalyzed Direct Substitution of the Hydroxy Group in Alcohols with Sulfonamides, Carbamates, and Carboxamides

Total Synthesis of Indotertine A and Drimentines A, F, and G

“…Finally, 20 a was subjected to SOCl 2 and pyridine at À90 8C, [26] producing drimentine G (2, 43 % yield) together with its D As shown in Scheme 5, treatment of drimentine F (3) with Bi(OTf) 3 /KPF 6 [27] smoothly rendered indotertine A (5, 78% yield), presumably through the path depicted in Scheme 1. The spectral and physical properties of the synthetic drimentines A, F, and G, and indotertine A were identical to those reported for the natural samples, which also verified their absolute configuration.…”

Calcium‐Catalyzed Direct Amination of π‐Activated Alcohols

“…As already mentioned in previous publications, [12,17] the formation of the highly reactive CaNTf 2 PF 6 species via anion exchange appears to be critical for an efficient conversion. Accordingly, a 1:1 stoichiometry of CaA C H T U N G T R E N N U N G (NTf 2 ) 2 and Bu 4 NPF 6 gives the best results.…”

“…[12] When the carbamate 5d was treated with 5 mol% CaA C H T U N G T R E N N U N G (NTf 2 ) 2 and 5 mol% Bu 4 NPF 6 in the presence of one equivalent of the tosylamide 4i an equilibrium between carbamate 4d and tosylamide 5i establishes over time.…”

“…Very recently, a first enantioselective direct amination of an allylic alcohol has been realized in an intramolecular fashion via the action of an HgA C H T U N G T R E N N U N G (OTf) 2 catalyst. [9] Some, mostly heterogeneous, Brønsted acid catalysts [10] were reported as well as rare earth metal-, [11] Bi-, [12,13] and iodinecatalyzed [14] protocols. However, the generally required harsh reaction conditions and extended reaction times limit the applicability of this type of transformation.…”

Direct Substitution of the Hydroxy Group at the Allylic/propargylic Position with Carbon‐ and Heteroatom‐ centered Nucleophiles Catalyzed by Yb(OTf)3

“…1 H NMR and 13 C NMR spectra were recorded on a Bruker 500 spectrometer using the residue of deuterated solvents as the internal standard, mass spectra were recorded by EI methods, GC-MS analysis was performed using a Hewlett Packard Model HP 6890 Series with HP-5 column. The reactions were monitored by TLC with Huanghai GF 254 silica gel.…”