Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 56, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202202015
Keywords
allenyne; alpha,3-dehydrotoluene; cycloaddition; cycloaromatization; selaginpuvilin A
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Funding
- NSF [CHE-2055055]
- NNSFC [21572163, 21873074]
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A new [4+2] cycloaddition reaction of allenyne-alkyne has been developed, proceeding with the formation of an alpha,3-dehydrotoluene intermediate. The reaction exhibits sigma pi-diradical reactivity with hydrogen atom donors and zwitterionic reactivity with weak nucleophiles.
A new [4+2] cycloaddition of allenyne-alkyne is developed. The reaction is believed to proceed with forming an alpha,3-dehydrotoluene intermediate. This species behaves as a sigma pi-diradical to react with a hydrogen atom donor, whereas it displays a zwitterionic reactivity toward weak nucleophiles. The efficiency of trapping alpha,3-dehydrotoluene depends not only on its substituents but also the trapping agents. Notable features of the reaction are the activating role of the extra alkyne of the 1,3-diyne that reacts with the allenyne moiety and the opposite mode of trapping with oxygen and nitrogen nucleophiles. Oxygen nucleophiles result in the oxygen-end incorporation at the benzylic position of the alpha,3-dehydrotoluene, whereas with amine nucleophiles the nitrogen-end is incorporated into the aromatic core. Relying on the allenyne-alkyne cycloaddition as an enabling strategy, a concise total synthesis of phosphodiesterase-4 inhibitory selaginpulvilin A is realized.
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