Spirocyclic oxetanes: Synthesis and properties

Angewandte Chemie - International Edition

Volumn 47, Issue 24, 2008, Pages 4512-4515

  Wuitschik, Georg ^b   Rogers Evans, Mark ^a   Buckl, Andreas ^b   Bernasconi, Maurizio ^b   Märki, Moritz ^b   Godel, Thierry ^a   Fischer, Holger ^a   Wagner, Björn ^a   Parrilla, Isabelle ^a   Schuler, Franz ^a   Schneider, Josef ^a   Alker, André ^a   Schweizer, W Bernd ^b   Müller, Klaus ^a   Carreira, Erick M ^b  

^a F HOFFMANN LA ROCHE LTD   (Switzerland)

^b ETH ZURICH   (Switzerland)

Author keywords

Carbonyl compounds; Heterocycles; Morpholine; Oxetanes; Spiro compounds

Indexed keywords

CARBONYLATION; ORGANIC LIGHT EMITTING DIODES (OLED); PHOTORESISTS; SYNTHESIS (CHEMICAL);

CARBONYL COMPOUNDS; HETEROCYCLES; MORPHOLINE; OXETANES; SPIRO COMPOUNDS;

CHEMICAL PROPERTIES;

ETHER DERIVATIVE; MORPHOLINE; MORPHOLINE DERIVATIVE; OXETANE;

ARTICLE; CHEMISTRY; CYCLIZATION; SOLUBILITY; SYNTHESIS;

CYCLIZATION; ETHERS, CYCLIC; MORPHOLINES; SOLUBILITY;

EID: 47149093553     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200800450     Document Type: Article

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20. 2O at a low pH value confirmed the exclusive existence of the N-axial configuration of the N-piperonyl group. Remarkably, a similar axial configuration was also found by X-ray crystal-structure analysis for the crystalline neutral base 8. By contrast, in the crystal structures of the neutral bases 7 and 3, the N-piperonyl group occupies an equatorial position. The preference for the axial orientation of the N substituent in 8 demonstrates a strong gauche driving effect for the C - C-(oxetane) - N - C backbone owing to the steric requirements of the bulky oxetane unit. This steric congestion is alleviated partially in the five- and four-membered rings as a result of the increased spatial separation between vicinal groups.
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