Catalytic diamination of olefins via N-N bond activation.

CONSPECTUS: Vicinal diamines are important structural motifs present in various biologically and chemically significant molecules. Direct diamination of olefins provides an effective approach to this class of compounds. Unlike well-established oxidation processes such as epoxidation, dihydroxylation, and aminohydroxylation, direct diamination of olefins had remained a long-standing challenge and had been less well developed.

Pd(0)-catalyzed sequential C-N bond formation via allylic and aromatic C-H amination of α-methylstyrenes with diaziridinone.

A novel Pd(0)-catalyzed sequential C-N bond formation process via allylic and aromatic C-H amination of α-methylstyrenes with di-tert-butyldiaziridinone, giving spirocyclic indolines in good yields, is described. Four C-N bonds and one spiro quaternary carbon are generated in a single operation.

Catalytic asymmetric synthesis of cyclic sulfamides from conjugated dienes.

This paper describes the catalytic asymmetric diamination of alkyl dienes using N,N'-di-tert-butylthiadiaziridine 1,1-dioxide in the presence of Pd(0) and a chiral phosphoramidite ligand to give cyclic sulfamides in high yield and high ee. The diamination is also amenable to gram scale.

A novel class of tunable cyclopropanation reagents (RXZnCH2Y) and their synthetic applications.

The Simmons-Smith cyclopropanation is a widely used method to synthesize cyclopropanes from alkenes using methylene iodide and a zinc reagent. A novel class of organozinc species, RXZnCH(2)Y, has been found to efficiently cyclopropanate alkenes, including traditionally unreactive unfunctionalized alkenes. The reactivity and selectivity of this class of organozinc reagents can be regulated by tuning the electronic and/or steric nature of the RX group attached to Zn.

Cu(I)-catalyzed diamination of conjugated dienes. Complementary regioselectivity from two distinct mechanistic pathways involving Cu(II) and Cu(III) species.

Conjugated dienes can be diaminated at the internal and/or terminal double bonds using Cu(I) as catalyst and N,N-di-t-butyldiaziridinone (1) as nitrogen source. The regioselectivity is highly dependent upon the choice of Cu(I) catalyst and the substituents on diene substrates. The diamination likely proceeds via two mechanistically distinct pathways.

Complementary regioselectivity in the Cu(I)-catalyzed diamination of conjugated dienes to form cyclic sulfamides.

This paper describes the regioselective diamination of conjugated dienes using inexpensive Cu(I) as catalyst and N,N-di-tert-butylthiadiaziridine 1,1-dioxide as nitrogen source. The regioselectivity of diamination is likely due to dual mechanistic pathways which are greatly influenced by reaction conditions and the nature of the diene. A variety of useful internal and terminal cyclic sulfamides can be obtained in good yield.