Abstract:A highly efficient one-pot synthesis of 3-azidopiperidines has been achieved by an intramolecular cyclization of unsaturated amines that allows for the nucleophilic installation of an azide moiety. This method unlocks the versatile employment of the azide functionality in the preparation and biological studies of piperidine-containing structures. This strategy has been expanded for the direct incorporation of a variety of nitrogen nucleophiles, and thus it provides a rapid and modular synthesis of 3-amino and … Show more
“…A number of representatives of this class exhibit glycosidase inhibitory activity or antimetastatic, anticancer, antitumour or anti-HIV properties [1–3]. A large number of natural products contain an indolizidine framework, among them (−)-δ-coniceine, (−)-swainsonine, indolizidine 167B [4–10], (+)-lentiginosine [11–15], (+)-slaframine [16], (−)-elaeokanine C [17], (+)-cyclizidine [18], lepadiformine [19], the highly oxygenated (+)-castanospermine [20–21], or pumiliotoxin [22]. Fig.…”
SummaryA novel stereocontrolled approach has been developed for the syntheses of tashiromine and epitashiromine alkaloids from cyclooctene β-amino acids. The synthetic concept is based on the azetidinone opening of a bicyclic β-lactam, followed by oxidative ring opening through ring C–C double bond and reductive ring-closure reactions of the cis- or trans-cyclooctene β-amino acids.
“…A number of representatives of this class exhibit glycosidase inhibitory activity or antimetastatic, anticancer, antitumour or anti-HIV properties [1–3]. A large number of natural products contain an indolizidine framework, among them (−)-δ-coniceine, (−)-swainsonine, indolizidine 167B [4–10], (+)-lentiginosine [11–15], (+)-slaframine [16], (−)-elaeokanine C [17], (+)-cyclizidine [18], lepadiformine [19], the highly oxygenated (+)-castanospermine [20–21], or pumiliotoxin [22]. Fig.…”
SummaryA novel stereocontrolled approach has been developed for the syntheses of tashiromine and epitashiromine alkaloids from cyclooctene β-amino acids. The synthetic concept is based on the azetidinone opening of a bicyclic β-lactam, followed by oxidative ring opening through ring C–C double bond and reductive ring-closure reactions of the cis- or trans-cyclooctene β-amino acids.
“…Interestingly, when N -chloroamine 11a , which is bench stable and can be isolated as a white solid, was treated with KI, we did not observe the formation of 11b via the ESI-MS study, but 126 or 127 was observed upon the treatment with KI, 12 , and Cs 2 CO 3 . This result suggests that the formation of 126 or 127 from a combination of 11 /NIS or 11 /NCS/KI might occur via different reaction mechanisms and chloroamine 11a did not undergo a simple chloride-iodide exchange process to form iodoamine 11b while such chloride-iodide exchange process is commonly proposed in literature 42 , 48 . Fig.…”
Saturated 1,4-diazo heterocycles including piperazines, 1,4-diazepanes, and 1,4-diazocanes, are highly important for therapeutic development, but their syntheses are often tedious. We describe here an amphoteric diamination strategy to unite readily available 1,2-, 1,3- or 1,4-diamine derivatives with electron-deficient allenes via a formal [n + 2] (n = 4, 5, 6) cyclization mode to produce the corresponding 1,4-diazo heterocycles in just one step. This strategy features mild reaction conditions, high functional group tolerance, and scalability (gram scale). The reagents used are cheap and readily available and no transition metal catalysts are needed. More sophisticated products containing trifluoromethyl group or bicyclic ring systems can be accessed via a one-pot procedure as well. Our mechanistic studies support that formation of mono-iodinated or chlorinated diamine intermediates is important for the desired transformation and the commonly proposed chloride-iodide exchange process and a radical N−C bond formation is unlikely when the combination of NCS/KI is used.
“…Very recently, Berhal and Prestat reported the aminocyclization/azidation of alkenyl oxy-ureas, oxy-carbamates, and oxy-amides with an [Fe(OAc) 2 /phenanthroline] catalytic system and TMSN 3 , giving azido-containing five-membered heterocyclic rings (Scheme , eq 3) . The NCS-promoted one-pot conversion of a series of unsaturated amines into the corresponding 3-azidopiperidines has been performed by Kang and co-workers in the presence of NaI and NaN 3 . Studer and a co-worker and Li and co-workers performed the intermolecular aminoazidations of olefins by copper and iron catalysis, respectively, using TMSN 3 in the presence of N -fluorobenzenesulfonimide .…”
The palladium-catalyzed
aminoazidation of aminoalkenes yielding
azidomethyl-substituted nitrogen-containing heterocycles was developed.
The procedure requires oxidative conditions and occurs at room temperature
in the presence of hydrogen peroxide and NaN3 as the azide
source. These conditions provide selective exo-cyclization/azidation
of the carbon–carbon double bond, furnishing a versatile approach
toward five-, six-, and seven-membered heterocyclic rings.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
