Reaction Pathways through a [1,5]‐Hydride Shift Triggered by Acids: Approach to Bridged‐Ring Heterocycles and Polycycles

The [1,5]‐hydride shift/cyclization process as a new Csp³–H bond functionalization has made tremendous advances over the past decades. Herein, we describe reaction pathways for a [1,5]‐hydride shift that is triggered by acid. In these transformations, the diene isoindoles are generated in situ and u...

Full description

Saved in:
Bibliographic Details
Published in:European journal of organic chemistry 2017-01, Vol.2017 (3), p.560-569
Main Authors: Zhen, Le, Dai, Liang, Yu, Sheng‐Qi, Lin, Chao, Sun, Hongbin, Xu, Qing‐Long
Format: Article
Language:English
Subjects:
Cycloaddition
Diastereoselectivity
Fused‐ring systems
Hydrides
Hydrogen bonds
Nitrogen heterocycles
Rearrangement
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The [1,5]‐hydride shift/cyclization process as a new Csp³–H bond functionalization has made tremendous advances over the past decades. Herein, we describe reaction pathways for a [1,5]‐hydride shift that is triggered by acid. In these transformations, the diene isoindoles are generated in situ and undergo a reaction with different dienophiles to provide access to a series of bridged‐ring heterocycles and polycycles in good yields (up to 94 %). In addition, we found that the choice of acid played a critical role and could be used to control the structure of the final product. An acid‐promoted [1,5]‐hydride shift strategy that occurs through a quinone methide (QM) formation/isomerization reaction sequence has been presented. The resulting intermediary isoindoles were further employed in intermolecular Diels–Alder reactions to give structurally diverse bridged‐ring heterocycles and polycyclic compounds. This method uses different acid catalysts to obtain different products.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201601319