Stereoselective Dynamic Cyclization of Allylic Azides: Synthesis of Tetralins, Chromanes, and Tetrahydroquinolines

Matthew R. Porter, Rami M. Shaker, Cristian Calcanas, Joseph J. Topczewski

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

This report describes the stereoselective synthesis of 3-azido-tetralins, -chromanes, and -tetrahydroquinolines via a tandem allylic azide rearrangement/Friedel-Crafts alkylation. Exposure of allylic azides with a pendant trichloroacetimidate to catalytic quantities of AgSbF6 proved optimal for this transformation. This cascade successfully differentiates the equilibrating azide isomers, providing products in excellent yield and selectivity (>25 examples, up to 94% yield and >25:1 dr). In many cases, the reactive isomer is only a trace fraction of the equilibrium mixture, keenly illustrating the dynamic nature of these systems. We demonstrate the utility of this process via a synthesis of hasubanan.

Original languageEnglish (US)
Pages (from-to)1211-1214
Number of pages4
JournalJournal of the American Chemical Society
Volume140
Issue number4
DOIs
StatePublished - Jan 31 2018

Bibliographical note

Funding Information:
We thank Ryan Daley for assistance in the analysis of compound 2d. Madeline D. Newcomb for creating the cover art associated with this manuscript. Financial support was provided by the University of Minnesota and The American Chemical Society’s Petroleum Research Fund (PRF # 56505-DNI1). This research was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Number R35GM124718. We also acknowledge NIH Shared Instrumentation Grant #S10OD011952.

Funding Information:
This research was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Number R35GM124718. We also acknowledge NIH Shared Instrumentation Grant #S10OD011952.

Publisher Copyright:
© 2018 American Chemical Society.

Fingerprint

Dive into the research topics of 'Stereoselective Dynamic Cyclization of Allylic Azides: Synthesis of Tetralins, Chromanes, and Tetrahydroquinolines'. Together they form a unique fingerprint.

Cite this