A domino aldol addition/hemiketal formation/hemiketal formation/epimerization route to a heteroadamantane. A crystal-structure, NMR, and computational study

Journal article


Publication Details

Author(s): Glaser H, Puchta R, van Eikema Hommes N, Leusser D, Murso A, Stalke D, Bauer W, Saalfrank R
Journal: Helvetica Chimica Acta
Publisher: Wiley-Blackwell
Publication year: 2002
Volume: 85
Journal issue: 11
Pages range: 3828-3841
ISSN: 0018-019X


Abstract


It has been found by serendipity during the attempted synthesis of the potential tris-bidentate ligand 7 that this compound undergoes multiple ring-closure reactions to form the heterodamantane derivative 12. This reaction involves a domino aldol addition/hemiketal formation/hemiketal formation/epimerization sequence. Compound 12 was studied intensively by X-ray crystal-structure analysis, NMR, and AM1 computations. Complete assignment of all H-1- and C-13-NMR signals was achieved by a combination of HMQC, HMBC, DPFGSE-NOE, COSY, and long-range-COSY experiments. The NMR data agreed well with the crystallographic and computational results. Accordingly, 12 is present as the thermodynamically most-stable diastereoisomer with relative u-configuration at centers C(8) and C(9). In summary, five stereogenic centers were created starting from an achiral precursor in an efficient cascade reaction under thermodynamic control.



FAU Authors / FAU Editors

Bauer, Walter apl. Prof. Dr.
Lehrstuhl für Organische Chemie II
Puchta, Ralph PD Dr.
Naturwissenschaftliche Fakultät
Saalfrank, Rolf Prof. Dr.
Naturwissenschaftliche Fakultät
van Eikema Hommes, Nico Dr.
Computer-Chemie-Centrum


How to cite

APA:
Glaser, H., Puchta, R., van Eikema Hommes, N., Leusser, D., Murso, A., Stalke, D.,... Saalfrank, R. (2002). A domino aldol addition/hemiketal formation/hemiketal formation/epimerization route to a heteroadamantane. A crystal-structure, NMR, and computational study. Helvetica Chimica Acta, 85(11), 3828-3841. https://dx.doi.org/10.1002/1522-2675(200211)85:11<3828::AID-HLCA3828>3.0.CO;2-Z

MLA:
Glaser, Horst, et al. "A domino aldol addition/hemiketal formation/hemiketal formation/epimerization route to a heteroadamantane. A crystal-structure, NMR, and computational study." Helvetica Chimica Acta 85.11 (2002): 3828-3841.

BibTeX: 

Last updated on 2018-19-04 at 03:17