The Reactions of 6-(Hydroxymethyl)-2,2-dimethyl-1-azaspiro[4.4]nonanes with Methanesulfonyl Chloride or PPh3-CBr4

The Reactions of 6-(Hydroxymethyl)-2,2-dimethyl-1-azaspiro[4.4]nonanes with Methanesulfonyl Chloride or PPh3-CBr4 Full article

Journal

Molecules
, E-ISSN: 1420-3049

Output data

Year: 2021, Volume: 26, Number: 19, Article number : 6000, Pages count : DOI: 10.3390/molecules26196000

Tags

Alkylation; Appel reaction; Azepane; Hofmann elimination; Nitroxide

Authors

Khoroshunova Y.V. ^1,2 , Morozov D.A. ¹ , Taratayko A.I. ^1,2 , Dobrynin S.A. ¹ , Eltsov I.V. ² , Rybalova T.V. ¹ , Sotnikova Y.S. ¹ , Polovyanenko D.N. ¹ , Asanbaeva N.B. ^1,2 , Kirilyuk I.A. ¹

Affiliations

1	N.N. Vorozhtsov Institute of Organic Chemistry SB RAS, Academician Lavrentiev Ave. 9, Novosibirsk, 630090, Russian Federation
2	Department of Natural Sciences, Novosibirsk State University, Pirogova Str. 1, Novosibirsk, 630090, Russian Federation

Activation of a hydroxyl group towards nucleophilic substitution via reaction with me-thanesulfonyl chloride or PPh3-CBr4 system is a commonly used pathway to various functional derivatives. The reactions of (5R(S),6R(S))-1-X-6-(hydroxymethyl)-2,2-dimethyl-1-azaspiro[4.4]nonanes 1a–d (Х = O·; H; OBn, OBz) with MsCl/NR3 or PPh3-CBr4 were studied. Depending on substituent X, the reaction afforded hexahy-dro-1H,6H-cyclopenta[c]pyrrolo[1,2-b]isoxazole (2) (for X = O), a mixture of 2 and octahydrocy-clopenta[c]azepines (4–6) (for X = OBn, OBz), or perhydro-cyclopenta[2,3]azeto[1,2-a]pyrrol (3) (for X = H) derivatives. Alkylation of the latter with MeI with subsequent Hofmann elimination afforded 2,3,3-trimethyl-1,2,3,4,5,7,8,8a-octahydrocyclopenta[c]azepine with 56% yield. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Khoroshunova Y.V. , Morozov D.A. , Taratayko A.I. , Dobrynin S.A. , Eltsov I.V. , Rybalova T.V. , Sotnikova Y.S. , Polovyanenko D.N. , Asanbaeva N.B. , Kirilyuk I.A.
The Reactions of 6-(Hydroxymethyl)-2,2-dimethyl-1-azaspiro[4.4]nonanes with Methanesulfonyl Chloride or PPh3-CBr4
Molecules. 2021. V.26. N19. 6000 . DOI: 10.3390/molecules26196000 WOS Scopus

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