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Synthesis 2020; 52(10): 1478-1497
DOI: 10.1055/s-0039-1690846
DOI: 10.1055/s-0039-1690846
short review
Structure, Reactivity, and Synthetic Applications of Sodium Diisopropylamide
We thank the National Institutes of Health (GM131713) for support.Further Information
Publication History
Received: 05 February 2020
Accepted: 08 February 2020
Publication Date:
23 March 2020 (online)
Abstract
The 60-year history of sodium diisopropylamide (NaDA) is described herein. We review various preparations, solvent-dependent stabilities, and solution structures. Synthetic applications of NaDA reported to date are framed by a mechanism-driven approach, emphasizing selectivities when appropriate. We conclude with examples beyond metalation in which NaDA plays a central role and with a few thoughts on where future applications could be focused.
1 Introduction
2 Preparation and Physical Properties
3 Solution Structures
4 Reactivity and Mechanism
4.1 Solvent Decomposition
4.2 Alkene and Diene Metalation
4.3 Arene Metalations
4.4 Dehydrohalogenations
5 Selectivity and Applications in Synthesis
5.1 Picoline Metalations
5.2 C–H Metalation
5.3 Dehydrohalogenations
5.4 Triflate Alkylation
5.5 Allyl Ether Isomerizations
5.6 Cyclic Allene Synthesis
5.7 Epoxide Elimination
5.8 Enolization
5.9 Orthometalation
6 Flow
7 Catalysis
8 Organosodium Salts and Secondary Applications
9 Conclusion
-
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We examined the efficacy of 2-ethylhexylsodium as a hydrocarbon-soluble alkylsodium and found it functional but inconvenient to manipulate, see:
For studies of base-mediated solvent decomposition, see:
For a recent application of NaDA-mediated 3-picoline functionalization, see:
For reviews on phase-transfer catalysis, see:
Inorganic chemists have found NaDA useful for installing the diisopropylamido moiety into transition-metal coordination spheres, see: