A Re(V)-Catalyzed C−N Bond-Forming Route to Human Lipoxygenase Inhibitors

Abstract

[reaction: see text] A regioselective synthesis of propargylamines by the coupling of propargyl alcohols with tosylamines and carbamates catalyzed by an air- and moisture-tolerant rhenium-oxo complex is described. The ability to couple functionalized components allows for convergent approaches to nitrogen-containing heterocyclic compounds such as the marine antibiotic pentabromopseudilin. These compounds were assayed against human lipoxygenase and found to be both potent and selective.

Transition metals in organic synthesis: Highlights for the year 2005

“…An iridium catalyzed N-allylation was used in a synthesis of (+)-and (−)-nicotine [681]. Rhenium catalyzed N-propargylation of amines with propargylic alcohols [682]. (92) Palladium catalyzed S-allylations of arenethiols [683] and of sodium phenylsulfinate [684] with allylic alcohols.…”

Enantioselective Copper‐Catalyzed Propargylic Amination

“…[5] Rhenium, gold, rhodium, and iron complexes were also reported recently to be effective catalysts for propargylic amination. [6] Remarkably, enantioselective examples of propargylic substitution reactions are rare, [7] and to our knowledge no asymmetric amination reaction has been reported to date. Inspired by the results of Murahashi and co-workers, we describe herein an enantioselective version of the copper-catalyzed propargylic amination of propargylic acetates.…”

“…The synthesis of ligands 1 and 6-8 is well documented, and 6, in particular, was obtained readily in only two steps from commercially available compounds. [10] An optimization study with ligand 6 revealed that other copper salts, such as [Cu(CH 3 CN) 4 ]PF 6 , CuOTf·benzene, and Cu(OAc) 2 , gave similar results, although CuI was slightly superior with respect to the selectivity ( Table 2, entries 1-3). High enantioselectivity and a high reaction rate were only observed with polar protic solvents, the best results with [a] Reaction conditions: 9 a (0.20 mmol), o-anisidine (0.40 mmol), DIPEA (0.80 mmol), CuI (0.02 mmol), and the ligand (0.024 mmol) were stirred in methanol (2 mL) at 25 8C.…”

Cationic Bismuth-Catalyzed Hydroamination and Direct Substitution of the Hydroxy Group in Alcohols with Amides

“…It is also noteworthy that the desired products were obtained using tertiary-propargyl alcohols 6r and 6s. Previously reported propargylic amination catalysts were not applied to tertiary-propargyl alcohols, possibly due to a competitive dehydration reaction to afford enynes [34,35]. The addition of Drierite was essential to obtain products 7rf and 7sa in >60% yield (Table 12, entries 3 and 4).…”