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Tandem 6pi-electrocyclization and cycloaddition of nitrodienes to yield multicyclic nitroso acetals.

ABSTRACT: 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.

SUBMITTER: Creech GS

PROVIDER: S-EPMC2903206 | biostudies-literature | 2010 Jul

REPOSITORIES: biostudies-literature

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Tandem 6pi-electrocyclization and cycloaddition of nitrodienes to yield multicyclic nitroso acetals.

Creech Gardner S GS Kwon Ohyun O

Journal of the American Chemical Society 20100701 26

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 ...[more]

PMID: 20557050

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