ISSN:
0009-2940
Keywords:
[2 + 2] Cycloaddition of 3,3-dimethylcyclopropene
;
Ring-anellated bicyclo[2.1.0]pentanes
;
Hydroxymercuration of bicyclo[2.1.0]pentanes
;
3,3-Dimethylcyclopentane anellation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Electrophilic Opening of Photochemically Generated Bicyclo-[2.1.0]pentane Derivative - A Two-Step 3,3-Dimethylcyclopentane AnellationTricyclic compounds 7a-e with 5,5-dimethylbicyclo[2.1.0]-pentane subunits were obtained - although in poor yields - by photochemically initiated [2 + 2] cycloaddition of 3,3-dimethylcyclopropene to 2-cycloalken-1-ones 4a-e. Catalytic hydrogenation of bicyclo[2.1.0]pentanes 7a/7c proceeded regioselectively to give bicyclic compounds 17a/17c with gem-dimethyl-substituted cyclopentane units. Treatment of carbonyl-protected bicyclo[2.1.0]pentanes 16a/16c with mercury(II) acetate in THF/water or THF/methanol followed by reductive demercuration afforded - with practically quantitative diastereo-, but no recognizable regioselectivity - gem-dimethyl-substituted hydroxy- or methoxycyclopentanes 18-21, respectively. Upon warming under reflux the hydroxymercurated ketone 7c gave the regioselectively formed β-elimination product endo-7-hydroxy-8,8-dimethylbicyclo[4.3.0]non-1(9)-en-2-one (23). Upon analogous treatment, however, hydroxymercurated 7a was recovered unchanged.
Notes:
Photochemisch initiierte [2 + 2]-Cycloaddition von 3,3-Dimethylcyclopropen an 2-Cycloalken-1-one 4a-e ergab - allerdings in mäßigen Ausbeuten - die Tricyclen 7a-e mit anellierten 5,5-Dimethylbicyclo[2.1.0]pentan-Einheiten. Die katalytische Hydrierung der Bicyclo[2.1.0]pentane 7a/7c verlief regioselektiv zu den Bicyclen 17a/17c mit gem-Dimethyl-substituierter, anellierter Cyclopentan-Einheit. Die Behandlung der Carbonyl-geschützten Bicyclo[2.1.0]pentane 16a/16c mit Quecksilber(II)-acetat in THF/Wasser oder THF/Methanol und nachfolgende reduktive Demercurierung lieferte die gem-Dimethyl-substituierten endo-Hydroxy- bzw. endo-Methoxycyclopentane 18-21 mit praktisch vollständiger Diastereo-, jedoch ohne erkennbare Regioselektivität. Hydroxymercuriertes 7c ergab nach Erwärmen das regioselektiv gebildete β-Eliminierungsprodukt endo-7-Hydroxy-8,8-dimethylbicyclo[4.3.0]non-1(9)-en-2-on (23). Bei analoger Behandlung wurde hydroxymercuriertes 7a unverändert zurückgewonnen.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19891220323
