@inbook{9b4712646dfa4ea7afa0f7506a5353a1,
title = "Synthesis of (±)-amathaspiramide F: Stereochemical switch of a [2,3]-stevens rearrangement",
abstract = "The total synthesis of complex natural products provides a unique opportunity for learning new lessons in chemical reactivity, which drives the field of synthesis forward. With this goal in mind, we describe our synthetic approach to (±)-amathaspiramide F, a polycyclic alkaloid. The key transformation in our strategy is a tandem palladium-catalyzed allylic amination/[2,3]-Stevens rearrangement, which was recently developed by our lab. Although our retrosynthetic analysis for the amathaspiramides was at first glance straightforward, we uncovered an unusual stereochemical effect that led us down an unexpected path to eventually solve the problem and complete the synthesis of amathaspiramide F. The unexpected diastereoselectivity of the [2,3]-Stevens rearrangement was controlled by the substitution patterns of an aromatic ring. This stereochemical switch may represent a new stereocontrolling element for [2,3]-sigmatropic rearrangements in complex molecular settings.",
keywords = "Alkaloid, Ammonium ylide, Diastereoselectivity, Palladium, [2,3]-rearrangement",
author = "Arash Soheili and Carrie Johnson and Tambar, {Uttam K.}",
note = "Funding Information: Financial support was provided by the W.W. Caruth, Jr. Endowed Scholarship, the Robert A. Welch Foundation (Grant I-1748), the National Science Foundation (NSF CAREER 1150875), and the Sloan Research Fellowship. We thank Aaron Nash (University of Texas Southwestern Medical Center) for experimental assistance and Dr. Vincent Lynch (University of Texas at Austin) for X-ray structural analysis.",
year = "2014",
doi = "10.1016/B978-0-12-417185-5.00006-5",
language = "English (US)",
isbn = "9780124171855",
series = "Strategies and Tactics in Organic Synthesis",
publisher = "Academic Press Inc.",
pages = "131--154",
booktitle = "Strategies and Tactics in Organic Synthesis",
}