A direct approach to β‐iodophosphonates and β‐iodophosphine oxides from 2,3‐dideoxy‐3‐phosphoryl carbohydrate derivatives has been achieved by using the anomeric alkoxyl radical 1,2‐fragmentation protocol. The reaction has been conducted on carbohydrate derivatives under mild conditions with (diacetoxyiodo)benzene and molecular iodine. Subsequent dehydroiodination afforded the corresponding vinylphosphonates and vinylphosphine oxides.

A mild, atom‐economic, and metal‐free α‐C−H amination of ethers using relatively stable nonafluorobutanesulfonyl (nonaflyl, Nf) azide as the aminating reagent to give N‐sulfonyl hemiaminals is reported. This enables unprecedented C(sp3) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.

A new general methodology for the synthesis of chiral vinylphosphonate and vinylphosphine oxide carbohydrate derivatives has been developed using the anomeric alkoxyl radical fragmentation reaction as the key step. The synthetic sequence proceeded via β-iodophosphonate and β-iodophosphine oxide intermediates, which may be interesting synthons for the introduction of phosphorus into organic molecules. These vinylphosphonates could be easily transformed into 2-methylene-1-phosphapentofuranoses (3-methylene-1,2-oxaphospholanes) and β-aminophosphonates, isosteres of biologically active α-methylene-γ-lactones and β-amino acids, respectively.

with a 4-deoxy-5-phosphapentopyranose framework. The structure and conformation of the 2-oxo-1,2-oxaphosphinane and 2-oxo-1,2-oxaphospholane ring systems in different carbohydrate models have been studied by NMR and X-ray crystallography.

Angularly and peri‐fused tricyclic pyrrolidinopyrazolines are efficiently prepared by LiCl‐catalyzed domino aza‐Michael addition‐1,3‐dipolar cycloaddition reactions. The absolute stereochemistry is controlled in the aza‐Michael addition step, nonaflyl azide serves as effective diazo transfer reagent to the formed enolate and the resulting diazo dipole engages in the 1,3‐dipolar cycloaddition step. The resulting tricyclic pyrrolidinopyrazolines can be easily transformed to enantiomerically enriched nonproteinogenic spirocyclic α,β,γ‐triamino acids, angularly or peri‐fused tricyclic β‐prolines or pyrimidines. The activity of the tricyclic amino acid derivatives against the hepatitis C virus was determined.