aza-di-π-methane rearrangement

https://doi.org/10.1351/goldbook.AT07329

Photochemical reaction of a 1-aza-1,4-diene or a 2-aza-1,4-diene in the triplet excited state to form the corresponding cyclopropylimine.

Note:
The @[email protected] formally amounts to a 1,2-shift of the imino group and 'bond formation' between the C(3) and C(5) carbon atoms of the azadiene skeleton. 1-Aza-1,[email protected]@ also undergo the @[email protected] to cyclopropylimines using electron-acceptor and electron-donor @[email protected] via [email protected]@ and [email protected]@ intermediates, respectively. 2-Aza-1,[email protected]@ rearrange to N-vinylaziridines on @[email protected] using electron-acceptor sensitizers. In this instance the reaction amounts to a 1,2-shift of the alkene unit and 'bond formation' between the C(1) and C(3) carbon atoms of the azadiene skeleton.

AT07329.png

See also: di-π-methane rearrangement, di-π-silane rearrangement, oxa-di-π-methane rearrangement

Source:
PAC, 2007, 79, 293. 'Glossary of terms used in photochemistry, 3rd edition (IUPAC Recommendations 2006)' on page 305 (https://doi.org/10.1351/pac200779030293)