Editorial pubs.acs.org/OPRD
Organometallic Carbanions in Practical Organic Synthesis: Grignards, Organolithiums, and More
O
rganometallic carbanions enjoy a place of privilege in synthetic chemistry; these are amongst the most useful synthons facilitating C−C bond formation. Relatively tricky and hazardous methodologies to execute at large scales, Grignard reactions and organolithiations are prime examples of chemistries that have become indispensable both in industry and academe. They have featured as the key C−C bond forming event in innumerable natural product and building block syntheses in academia. From basic intermediates to late stage active ingredients, organometallic carbanions have led to robust, efficient, and cost-competitive manufacturing processes across the entire spectrum of the chemical industry. It is our pleasure to bring you this special feature in Organic Process Research & Development for organometallic carbanions in practical organic synthesis. The feature is anchored by a mammoth review from Terry Rathman and James Schwindeman on the physicochemical properties of commercial organolithiums for their optimal use and safe handling. Gerald Tanoury and co-workers subsequently demonstrate several aspects from this review in real life in their manuscript that showcases a stereoselective lithiation/carboxylation at the multihundred kilogram scale. Industrial scale syntheses of several liquid crystal intermediates via fluorine-directed ortholithiation are detailed in a manuscript by Ruimao Hua and coworkers. An intramolecular arylation of lithiated ureas is highlighted by Jonathan Clayden and co-workers. In the first of two manuscripts, Steven Ley and co-workers describe the design and application of a flow reactor platform for conducting organometallic carbanion chemistry in the continuous regime. Their accompanying manuscript details the modification of the same reactor system to allow for extended reaction periods and larger scale processing for a fluorine-directed ortho-lithiation application. Finally, a Grignard addition to a trifluoromethyl ketone is also adapted to the continuous regime by Nicholas Leadbeater and co-workers. From the seminal work of Victor Grignard leading to his Nobel Prize in 1912 to being a disconnection of choice in the classroom, the university laboratory, and the manufacturing plant, organometallic carbanion chemistry has indeed come a long way and continues apace. We hope you enjoy this special feature!
Aman A. Desai
Aether Industries Limited, Surat 394230, Gujarat, India. E-mail:
[email protected].
Victor Snieckus
■
Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6, Canada. E-mail: Victor.Snieckus@ chem.queensu.ca.
AUTHOR INFORMATION
Notes
Special Issue: Organometallic Carbanions in Practical Organic Synthesis
Views expressed in this editorial are those of the author and not necessarily the views of the ACS. © 2014 American Chemical Society
Published: October 17, 2014 1191
dx.doi.org/10.1021/op500283p | Org. Process Res. Dev. 2014, 18, 1191−1191
