Aeyad, T., Williams, J.D., Meijer, A.J.H.M. orcid.org/0000-0003-4803-3488 et al. (1 more author) (2017) Lithiation–Substitution of N -Boc-2-phenylazepane. Synlett, 28 (20). pp. 2765-2768. ISSN 0936-5214
Abstract
Preparation of 2,2-disubstituted azepanes was accomplished from N - tert -butoxy( N -Boc)-2-phenylazepane by treatment with butyllithium then electrophilic quench. The lithiation was followed by in situ ReactIR spectroscopy and the rate of rotation of the carbamate was determined by variable temperature (VT)-NMR spectroscopy and by DFT studies. Most electrophiles add α to the nitrogen atom but cyanoformates and chloroformates gave ortho -substituted products. Cyclic carbamates were formed from an aldehyde or ketone electrophile. Kinetic resolution with sparteine was only poorly selective. Removal of the Boc group promoted cyclization to a homoindolizidine or an isoindolinone.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 Georg Thieme Verlag. This is an author produced version of a paper subsequently published in SYNLETT. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | alkylation; heterocycles; lithiation; lithium |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 06 Sep 2017 09:56 |
Last Modified: | 14 Dec 2023 12:06 |
Published Version: | https://doi.org/10.1055/s-0036-1590857 |
Status: | Published |
Publisher: | Georg Thieme Verlag |
Refereed: | Yes |
Identification Number: | 10.1055/s-0036-1590857 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:120839 |