General Allylic C–H Alkylation with Tertiary Nucleophiles

A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium­(II)/bis­(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2014-04, Vol.136 (15), p.5750-5754
Main Authors: Howell, Jennifer M, Liu, Wei, Young, Andrew J, White, M. Christina
Format: Article
Language:English
Subjects:
Aliphatic compounds
Alkylation
Carbon - chemistry
Cascades
Dienes
Esters
Hydrocarbons - chemistry
Hydrogen - chemistry
Nucleophiles
Olefins
Proton Magnetic Resonance Spectroscopy
Stereoselectivity
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:A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium­(II)/bis­(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja500726e