Conventional approaches on using hydroxylamine derivatives as single nitrogen sources, for the construction of n-membered (n > 3) N-heterocycles, rely upon two chemical operations by involving sequential nucleophilic and electrophilic C–N bond formations. Here, we report a highly efficient cascade alkyne insertion/C–H activation/amination rapid preparation myriad tricyclic indoles, in single-step transformation, bifunctional secondary hydroxylamines. It is noteworthy that judicious selection...

Abstract The novel tricyclic spiroketal alotane‐type sesterterpenoids showed strikingly different biological activities and potency with subtle structural alterations. Asymmetric total syntheses of the (−)‐alotaketals A–D (−)‐phorbaketal A were accomplished [29–31 steps from (−)‐malic acid] in a collective way for first time. key features strategy included 1) new cascade cyclization vinyl epoxy δ‐keto‐alcohols to forge common intermediate, 2) late‐stage allylic C−H oxidation, 3) olefin...

Abstract Ansellane‐type sesterterpenoids including, ansellones A‐G and (+)‐phorbadione are structurally novel marine secondary metabolites which exhibit anticancer anti‐HIV activity. The first, asymmetric total syntheses of three representative members, (−)‐ansellones A B (+)‐phorbadione, were accomplished in 16–23 steps from (+)‐sclareolide. route features the first regioselective cyclization vinyl epoxides with internal alcohol nucleophiles a 1,4‐addition manner (S N 2′). Additionally,...

Two routes were developed for the catalytic asymmetric total synthesis of tetrahydroprotoberberine alkaloids.

The first cross-coupling reaction between aryl silanes and boronic acids is described. This transformation represents one of the very few examples coupling reactions two nucleophilic organometallic reagents provides a new method for formation biaryl compounds. successful development this was enabled by use commercially available 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) as ligand. A small amount BINAP (3 mol %) sufficient to suppress homocoupling products, yielded products with...

A dearomatization/deiodination/rearomatization strategy for the [3 + 2] cyclization of o-iodophenolic substrates with α,β-unsaturated imines to construct various dihydrobenzofuran-related skeletons has been established. Tolerance different functional groups tested. Mechanistic studies revealed that this domino reaction was possibly realized by deiodination and tautomerization key dearomatized intermediate generate a free phenolic O radical. Moreover, an anticancer agent 4 α-glucosidase...

Abstract The copper‐catalyzed decarboxylative methylation of aromatic carboxylic acids was developed by using PhI(OAc) 2 to provide a new strategy for the aryl through decarboxylation alkyl acids. mechanism and roles each reactant in reaction were investigated extensively.

Development of two novel oxa-[3 + 2] cycloaddition reactions Achmatowicz products with 1,3-dicarbonyl compounds for rapid and highly efficient assembly polycyclic furopyranones is described. Plausible mechanisms were proposed.

Abstract The novel tricyclic spiroketal alotane‐type sesterterpenoids showed strikingly different biological activities and potency with subtle structural alterations. Asymmetric total syntheses of the (−)‐alotaketals A–D (−)‐phorbaketal A were accomplished [29–31 steps from (−)‐malic acid] in a collective way for first time. key features strategy included 1) new cascade cyclization vinyl epoxy δ‐keto‐alcohols to forge common intermediate, 2) late‐stage allylic C−H oxidation, 3) olefin...

Abstract Transition-metal-catalyzed C–N bond formation is one of the most important pathways to synthesize N-heterocycles. Hydroxylamines can be transformed into a nucleophilic reagent react with carbon cation or coordinate transition metal; it also become an electrophilic nitrogen source arenes, alkenes, and alkynes. In this short review, progress made on transition-metal-catalyzed cycloadditions hydroxylamines as summarized. 1 Introduction 2 Cycloaddition To Form Aziridine Derivatives 2.1...

Abstract Ansellane‐type sesterterpenoids including, ansellones A‐G and (+)‐phorbadione are structurally novel marine secondary metabolites which exhibit anticancer anti‐HIV activity. The first, asymmetric total syntheses of three representative members, (−)‐ansellones A B (+)‐phorbadione, were accomplished in 16–23 steps from (+)‐sclareolide. route features the first regioselective cyclization vinyl epoxides with internal alcohol nucleophiles a 1,4‐addition manner (S N 2′). Additionally,...

Abstract The first cross‐coupling reaction between aryl silanes and boronic acids is described. This transformation represents one of the very few examples coupling reactions two nucleophilic organometallic reagents provides a new method for formation biaryl compounds. successful development this was enabled by use commercially available 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) as ligand. A small amount BINAP (3 mol %) sufficient to suppress homocoupling products, yielded products...

Conventional approaches on using hydroxylamine derivatives as single nitrogen sources, for the preparation of N-heterocyclic molecules, rely upon two chemical operations by involving sequential nucleophilic and electrophilic C−N bond formations. Here, we report a novel Suzuki reaction/C−H activation/amination sequence building up myriad carbazoles, in transformation, bifunctional secondary hydroxylamines. Noteworthy, synthetic utility this methodology is highlighted with total synthesis...

Comprehensive Summary A general and efficient strategy for the synthesis of γ ‐lactams has been reported. The hydroxylamines form Lossen rearrangement products electron‐deficient group migration with base then undergo [3+2] cycloaddition reaction vinyl cyclopropane, which could be performed broad substrate scope, excellent functional tolerance high efficiency to produce desired products. It also allowed further modification other derivatives these γ‐lactams.

Abstract Depending on the reaction conditions, either annulated furo[3,2‐b]pyran or furo[2,3‐b]pyran scaffolds are highly diastereoselectively obtained.

Abstract Oxidative coupling of trialkoxyarylsilanes with areneboronates gives various biaryls.

Abstract Imidoyl chloride intermediates, generated by isocyanide‐Nef reaction of acyl chlorides and phosphorane (II), undergo sequential dehydrochlorination/intramolecular aza‐Wittig with carboxylic acids to give the title compounds.