Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 51, Pages 26762-26768Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202111708
Keywords
cyclopentadienone; HOMO activation; tropone; umpolung; pi-Lewis base catalysis
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Funding
- Natural Science Foundation of China [21971166, 21931006, 21772126, 21921002]
- National Key Research and Development Program of China [2018YFA0507900]
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The study reveals that carbonates of 4-hydroxy-2-cyclopentenones can form unique palladium complexes for inverse-electron-demand aza-Diels-Alder reactions, along with the synthesis of chiral cycloadducts through cross Rauhut-Currier addition. Additionally, new chiral ligands have been developed for high stereoselectivity even with racemic substrates.
We disclose that the carbonates of 4-hydroxy-2-cyclopentenones can form pi-allylpalladium-based 1,2-carbodipoles, which isomerize to interesting eta(2)-Pd-0-cyclopentadienone complexes. Compared with the labile parent cyclopentadienone, the HOMO energy of the related eta(2)-complex was significantly raised via the back-bonding of Pd-0 as a pi-Lewis base, rendering the uncoordinated C=C bond an electron-richer dienophile in inverse-electron-demand aza-Diels-Alder-type reactions with diverse 1-azadienes. The vinylogous (aza)Morita-Baylis-Hillman or cross Rauhut-Currier addition to (imine)carbonyls or activated alkenes, respectively, was also realized to afford chiral [4+2] or [2+2] cycloadducts, respectively, after trapping the re-generated pi-allylpalladium species. New C-1-symmetric ligands from simple chiral sources were developed, exhibiting high stereoselectivity even with racemic substrates via an unusual dynamic kinetic resolution process. Besides, tropone could be similarly activated by a Pd-0 complex.
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