Palladium(II)-Catalyzed Allylic CH Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation

Angewandte Chemie - International Edition

Volumn 54, Issue 38, 2015, Pages 11186-11190

  Xing, Xiangyou ^a   O'Connor, Nicholas R ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

allylic compounds; C H functionalization; heterocycles; oxidation; palladium

Indexed keywords

AMIDES; OXIDATION; PALLADIUM;

ALLYLIC ACETATES; ALLYLIC COMPOUNDS; DOMINANT PRODUCT; EFFECTIVE SYSTEMS; FUNCTIONALIZATIONS; HETEROCYCLES; SYNTHETIC UTILITY; TWO-ELECTRON OXIDATION;

PALLADIUM COMPOUNDS;

EID: 84938257497     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201504007     Document Type: Article

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65. Substrates incorporating terminal olefins (7 s and 7 t), provided inseparable mixtures of multiple oxidation products upon subjection to either the allylic acetoxylation or enal formation conditions. The mixtures included allylic acetates, enals, methyl ketones, and other compounds.
66. The β-lactam substrate 7 u provided a mixture of the allylic acetate, enal, and methyl ketone products upon treatment with the conditions for allylic acetoxylation. The same substrate furnished only the methyl ketone product 16 in moderate yield upon subjection to the enal conditions.
67. It is possible that both the allylic acetate and enal products are formed through a palladium(II)-π-allyl intermediate, although other pathways, particularly Wacker-type activation of the olefin, may also be envisioned. The requirement of an electron-rich lactam moiety in the substrate suggests intramolecular direction may play a role in the mechanism. Control experiments show that both the allylic alcohol and the aliphatic aldehyde are smoothly converted to the enal, indicating that either could serve as a mechanistic intermediate. See the Supporting Information for details.
68. Although it is clear that the allylic oxidation chemistry reported herein has certain scope limitations, the complete applicability of these new conditions for CH functionalization is not yet fully realized. For example, we recently found that exposure of (S)-carvone (17) to similar reaction conditions resulted in selective allylic acetoxylation in moderate yield. See the Supporting Information for details.