Regioselectivity Switch in Palladium‐Catalyzed Allenylic Cycloadditions of Allenic Esters: [4+1] or [4+3] Cycloaddition/Cross‐Coupling

The first Pd‐catalyzed asymmetric allenylic [4+1] cycloaddition was successfully developed. Alternatively, tuning the Pd catalyst switched the reactivity toward an unprecedented [4+3] cycloaddition/cross‐coupling. Ligands play a vital role in controlling the reaction pathway, allowing highly selecti...

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Published inAngewandte Chemie International Edition Vol. 58; no. 14; pp. 4710 - 4713
Main Authors Li, Long, Luo, Pengfei, Deng, Yuhua, Shao, Zhihui
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 26.03.2019
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Antitumor activity
Catalysis
Chemistry
Chemistry, Multidisciplinary
Coupling
Cycloaddition
dendralenes
Esters
ligands
Palladium
Physical Sciences
reaction mechanisms
Regioselectivity
Science & Technology
Substrates
ligands
cycloaddition
ASYMMETRIC-SYNTHESIS
SPIROPYRAZOLONES
ANNULATION
dendralenes
reaction mechanisms
REACTIVITY
palladium
GENERATION
YLIDES
ISOXAZOLINONES
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Summary:The first Pd‐catalyzed asymmetric allenylic [4+1] cycloaddition was successfully developed. Alternatively, tuning the Pd catalyst switched the reactivity toward an unprecedented [4+3] cycloaddition/cross‐coupling. Ligands play a vital role in controlling the reaction pathway, allowing highly selective access to different products from identical substrates. Biological evaluation of the obtained compounds led to the discovery of new antitumor targets. A possible mechanism is proposed, suggesting two interesting catalytic cycles for the cycloaddition with palladium‐butadienyls. This study also demonstrated the potential and utility of allenic esters as 1,4‐biselectrophiles and C4 synthons for participating in cycloaddition reactions. Switch it: The use of metal‐butadienyl species in a cycloaddition is exemplified by the first Pd‐catalyzed asymmetric allenylic [4+1] cycloaddition. Notably, tuning the Pd catalysts switched the reactivity toward an unprecedented [4+3] cycloaddition/cross‐coupling. These reactions lead to diverse and valuable carbocycles and heterocycles, and also provide a straightforward synthesis to [3]dendralenes.
Bibliography:Dedicated to Professor Shengming Ma
These authors contributed equally to this work.
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 14
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201901511