On the control of secondary carbanion structure utilising ligand effects during directed metallation

Wheatley, Andrew E.H.; Clayden, Jonathan; Hillier, Ian H.; Campbell Smith, Alison; Vincent, Mark A.; Taylor, Laurence J.; Haywood, Joanna

Abstract

N,N-Diisopropyl-2-propylbenzamide 6-H undergoes lateral deprotonation by t-BuLi in the presence of the Lewis base PMDTA (N,N,N′,N″,N″-pentamethyldiethylenetriamine) to give a benzyllithium 6-Lil·PMDTA that incorporates a trigonal planar secondary carbanion. In the solid state, the amide directing group and the PMDTA additive work together to abstract the metal ion from the deprotonated α-C of the propyl group (4.107(4) Å). A short distance of 1.376(3) Å is observed between the deprotonated carbon centre and a planar aromatic system that shows a pattern of bond lengths which contrasts with that reported for related tertiary carbanion systems. Analogous benzylic deprotonation is seen if 6-H is treated with t-BuLi in the presence of diglyme to give 6-Lil·DGME. X-ray crystallography now shows that the metal ion more closely approaches the tertiary carbanion (2.418(6) Å) but that the planarity of the deprotonated carbon centre and the bonding pattern in the organic anion seen in the PMDTA complex are retained. DFT analysis corroborates both the short distance between aromatic ring and carbanion centre and the unperturbed nature of aromaticity in 6-Lil·L (L = Lewis base). The observation of two structure-types for the carbanion in solution is explained theoretically and by NMR spectroscopy in terms of cis and trans isomerism imparted by partial double bond character in the arene–(α-C) bond.

Citation

Wheatley, A. E., Clayden, J., Hillier, I. H., Campbell Smith, A., Vincent, M. A., Taylor, L. J., & Haywood, J. (2012). On the control of secondary carbanion structure utilising ligand effects during directed metallation. Beilstein Journal of Organic Chemistry, 8, 50-60. https://doi.org/10.3762/bjoc.8.5

• Journal Article Type: Article
• Acceptance Date: Dec 15, 2011
• Online Publication Date: Jan 9, 2012
• Publication Date: Jan 9, 2012
• Deposit Date: Apr 24, 2023
• Publicly Available Date: Apr 26, 2023
• Journal: Beilstein Journal of Organic Chemistry
• Print ISSN: 1860-5397
• Electronic ISSN: 1860-5397
• Publisher: Beilstein-Institut
• Peer Reviewed: Peer Reviewed
• Volume: 8
• Pages: 50-60
• DOI: https://doi.org/10.3762/bjoc.8.5
• Public URL: https://nottingham-repository.worktribe.com/output/19789443
• Publisher URL: https://www.beilstein-journals.org/bjoc/articles/8/5