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Bicyclic Sultams with a Nitrogen at the Bridgehead and a Sulfur Atom in the Apex Position: Facile Preparation and Conformational Properties
Author(s) -
Rassadin Valentin A.,
Grosheva Daria S.,
Tomashevskiy Aleksandr A.,
Sokolov Viktor V.,
Yufit Dmitry S.,
Kozhushkov Sergei I.,
de Meijere Armin
Publication year - 2010
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201000345
Subject(s) - bicyclic molecule , chemistry , nonane , octane , intramolecular force , yield (engineering) , nitrogen atom , heptane , sulfur , alkylation , derivative (finance) , stereochemistry , organic chemistry , ring (chemistry) , catalysis , materials science , economics , financial economics , metallurgy
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 K 2 CO 3 /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.