In:
Angewandte Chemie International Edition, Wiley, Vol. 60, No. 51 ( 2021-12-13), p. 26762-26768
Abstract:
We disclose that the carbonates of 4‐hydroxy‐2‐cyclopentenones can form π‐allylpalladium‐based 1,2‐carbodipoles, which isomerize to interesting η 2 ‐Pd 0 ‐cyclopentadienone complexes. Compared with the labile parent cyclopentadienone, the HOMO energy of the related η 2 ‐complex was significantly raised via the back‐bonding of Pd 0 as a π‐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 π‐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.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202111708
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7