Tandem 6pi-electrocyclization and cycloaddition of nitrodienes to yield multicyclic nitroso acetals.
Upon heating, nitrodienes rearrange through 6pi-electrocyclization to form nitronate intermediates, which can be captured through tandem [3 + 2] dipolar cycloadditions to form highly functionalized nitroso acetals. The one-pot, two-step domino process is highly efficient, proceeding with good facial selectivity and exoselectivity. Dipolarophiles featuring electron-rich, -neutral, and -deficient carbon-carbon double bonds are viable substrates for [3 + 2] cycloadditions with the in situ generated nitronates. In addition, the highly functionalized nitroso acetal products can be hydrogenolyzed selectively to form densely functionalized spirocyclic hydroxy amides or hydroxy gamma-amino acids.
Creech
Gardner S
GS
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Kwon
Ohyun
O
D000080:Acetals / Q000737:chemistry*; D003500:Cyclization; D009603:Nitroso Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000080:Acetals; D009603:Nitroso Compounds