Stereoselectivity of Additions to N-Methyl Acetonitrilium Fluorosulfonate

Keese, Reinhart; Berdat, Francois; Macchi, Piero (2013). Stereoselectivity of Additions to N-Methyl Acetonitrilium Fluorosulfonate. Journal of organic chemistry, 78(5), pp. 1965-1970. American Chemical Society 10.1021/jo301983s

[img] Text
82_RK_2013.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (366kB) | Request a copy

Alkoxy-N-methyl-acetiminium salts were prepared by addition of CH3OH and C2H5OH to N-methyl acetonitrilium fluorosulfonate at low temperature. Analysis of the (5)J(HH) and (3)J(13)C-H coupling constants in the NMR spectra showed an anti addition with a diastereoselectivity of >9596. Deprotonation of these salts with (Z)-configuration gave the corresponding N-methyl-alkoxyacetimines with very high (E)-configuration. Upon protonation at -78 degrees C, these iminoesters gave the corresponding alkoxy-N-methyl-acetirninium salts with (E)-configuration. Computational analyses of the iminoesters and the corresponding iminium cations including the conformations give insight into the relative stability. Nitrilium salts can be used as reagents, exemplified by some esterifications between simple acids and alcohols.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Other Institutions > Emeriti, Faculty of Science
08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Keese, Reinhart and Macchi, Piero

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0022-3263

Publisher:

American Chemical Society

Language:

English

Submitter:

Piero Macchi

Date Deposited:

10 Apr 2014 15:12

Last Modified:

27 Aug 2015 10:21

Publisher DOI:

10.1021/jo301983s

BORIS DOI:

10.7892/boris.45661

URI:

https://boris.unibe.ch/id/eprint/45661

Actions (login required)

Edit item Edit item
Provide Feedback