Projects per year
Abstract
Equipped with excellent hydrocarbon solubility, the lithium hydride surrogate 1-lithium-2-t-butyl-1,2-dihydropyridine (1tLi) functions as a precatalyst to convert Me2NH·BH3 to [NMe2BH2]2 (89% conversion) under competitive conditions (2.5 mol%, 60h, 80°C, toluene solvent) to that of previously reported LiN(SiMe3)2. Sodium and potassium dihydropyridine congeners produce similar high yields of [NMe2BH2]2 but require longer times. Switching the solvent to pyridine induces a remarkable change in the dehydrocoupling product ratio, with (NMe2)2BH favoured over [NMe2BH2]2 (e.g., 94%:2% for 1tLi). Demonstrating its versatility, precatalyst 1tLi was also successful in promoting hydroboration reactions between pinacolborane and a selection of aldehydes and ketones. Most reactions gave near quantitative conversion to the hydroborated products in 15 minutes, though sterically demanding carbonyl substrates require longer times. The mechanisms of these rare examples of group 1 metal catalysed processes are discussed.
Original language | English |
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Pages (from-to) | 16853-16861 |
Number of pages | 9 |
Journal | Chemistry - A European Journal |
Volume | 23 |
Issue number | 66 |
Early online date | 21 Sep 2017 |
DOIs | |
Publication status | Published - 27 Nov 2017 |
Keywords
- soluble hydride surrogates
- 1-lithium-2-t-butyl-1,2-dihydropyridine
- 1tLi
Fingerprint
Dive into the research topics of '1-Alkali-metal-2-alkyl-1,2-dihydropyridines: soluble hydride surrogates for catalytic dehydrogenative coupling and hydroboration applications'. Together they form a unique fingerprint.Profiles
Projects
- 2 Finished
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EPSRC Doctoral Training Grant - DTA, University of Strathclyde | Orr, Samantha Alana
Mulvey, R., O'Hara, C. & Orr, S. A.
EPSRC (Engineering and Physical Sciences Research Council)
1/10/13 → 20/09/17
Project: Research Studentship - Internally Allocated
Datasets
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Data for: "1-Alkali-metal-2-alkyl-1,2-dihydropyridines: soluble hydride surrogates for catalytic dehydrogenative coupling and hydroboration applications"
Robertson, S. (Creator), Mulvey, R. (Creator), McLellan, R. (Contributor), Kennedy, A. (Contributor) & Orr, S. A. (Contributor), University of Strathclyde, 14 Oct 2017
DOI: 10.15129/f26d3563-55d1-47a6-860c-a2fa8e643c26
Dataset
Activities
- 2 Invited talk
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Alkali metal mediation in synergistic synthesis and catalysis
Robert Mulvey (Speaker)
16 Nov 2017Activity: Talk or presentation types › Invited talk
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Main group dihydropyridine surrogate hydrides: synthesis, structures, reactivity and catalytic applications
Robert Mulvey (Speaker)
23 Aug 2017Activity: Talk or presentation types › Invited talk