Bicyclic Sultams with a Nitrogen at the Bridgehead and a Sulfur Atom in the Apex Position: Facile Preparation and Conformational Properties

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 18; pp. 3481 - 3486
• Main Authors: Rassadin, Valentin A., Grosheva, Daria S., Tomashevskiy, Aleksandr A., Sokolov, Viktor V., Yufit, Dmitry S., Kozhushkov, Sergei I., de Meijere, Armin
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-06-2010; WILEY‐VCH Verlag; Wiley-VCH
• Subjects: Bridged sultams; Conformational analysis; Cyclization; Oxidative deprotection; Solid-state structures
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201000345

A practical synthesis of bicyclic sultams with a pyramidal bridgehead nitrogen atom and a sulfur atom in the apex position has been elaborated. Compounds with 1‐azathiabicyclo[2.2.1]heptane (12a), ‐bicyclo[3.2.1]octane (12b, 12d), and ‐bicyclo[3.3.1]nonane (13b) skeletons were obtained by direct twofold inter/intramolecular alkylation of corresponding monocyclic sultams 9 and 10 with α,ω‐dihalides 11 in K2CO3/DMF in 56, 68, 52 and 52 % yield, respectively. On the other hand, a 1‐aza‐9‐thiabicyclo[4.2.1]nonane derivative (12c) could be prepared only by stepwise dialkylation in 24 % overall yield. Structural and conformational properties of four of the newly prepared bicyclic sultams in solution as well as in the solid state are discussed.
Bicyclic sultams with 1‐azathiabicyclo[2.2.1]heptane, ‐bicyclo[3.2.1]octane, and‐bicyclo[3.3.1]nonane skeletons have been prepared by direct twofold inter/intramolecular alkylation of corresponding monocyclic sultams with α,ω‐dihalides in 56, 68, 52 and 52 % yield.