Continuous Flow Magnesiation or Zincation of Acrylonitriles, Acrylates, and Nitroolefins. Application to the Synthesis of Butenolides

Maximilian A Ganiek; Matthias R Becker; Marthe Ketels; Paul Knochel

doi:10.1021/acs.orglett.6b00086

Continuous Flow Magnesiation or Zincation of Acrylonitriles, Acrylates, and Nitroolefins. Application to the Synthesis of Butenolides

Org Lett. 2016 Feb 19;18(4):828-31. doi: 10.1021/acs.orglett.6b00086. Epub 2016 Feb 10.

Authors

Maximilian A Ganiek¹, Matthias R Becker¹, Marthe Ketels¹, Paul Knochel¹

Affiliation

¹ Department of Chemistry, Ludwig-Maximilians-Universität , Butenandtstr. 5-13, 81377 Munich, Germany.

PMID: 26863289
DOI: 10.1021/acs.orglett.6b00086

Abstract

Scalable continuous flow procedures are reported for the metalation and downstream functionalization of β-substituted acrylates. The flow conditions allow the metalation of acrylonitriles, acrylates, and nitroolefins at 0.25-2.50 mmol/min conversion rates. Magnesiations can be performed with short residence times (1-20 min) and near-ambient temperature using TMPMgCl·LiCl. Further, high temperature zincation (≤90 °C) using TMPZnCl·LiCl is possible. This method allows a simple entry to 2(5H)-furanones by flow generation of magnesiated acrylates and a subsequent reaction with aldehydes.

Publication types

Research Support, Non-U.S. Gov't