768-50-3Relevant academic research and scientific papers
Catalytic Multisite-Selective Acetoxylation Reactions at sp2 vs sp3 C-H Bonds in Cyclic Olefins
Zang, Zhong-Lin,Zhao, Sheng,Karnakanti, Shuklachary,Liu, Cheng-Lin,Shao, Pan-Lin,He, Yun
, p. 5014 - 5017 (2016/10/14)
The first Pd-catalyzed multisite-selective acetoxylation reactions are disclosed at an unactivated alkene sp2 C-H bond versus secondary allylic sp3 C-H bond in cyclic olefins via the modulation of directing groups. The different directing groups overcome the key challenge in differentiating C-H bonds and provide a new controlling approach for site-specific C-H activation. A wide variety of substrates are readily acetoxylated under operationally simple conditions. Mechanistic studies suggest that different Pd (IV) intermediates were involved in the multisite-selective acetoxylation reactions.
3-alkoxy-1,2-dioxolanes: Synthesis and evaluation as potential antimalarial agents
Schiaffo, Charles E.,Rottman, Matthias,Wittlin, Sergio,Dussault, Patrick H.
scheme or table, p. 316 - 319 (2011/06/19)
A number of 3-alkoxy-1,2-dioxolanes exhibit promising levels of antimalarial activity against Plasmodium falciparum. A new route to the 1,2-dioxolane core is reported based on tandem peroxidation/cyclization of enones.
Stereoselective synthesis of β,γ-unsaturated ketones by acid-mediated Julia-type transformation from 2-(1-hydroxyalkyl)-1- alkylcyclopropanols
Nomura, Kenichi,Matsubara, Seijiro
experimental part, p. 1412 - 1414 (2009/04/06)
An efficient transformation of 2-(1-hydroxyalkyl)-1-alkylcyclopropanols, obtained from α,β-unsaturated ketones, to β,γ-unsaturated ketones was achieved by trifluoroacetic acid (TFA)-mediated reaction. Georg Thieme Verlag Stuttgart.
Catalytic reactions of metalloporphyrins. II. Activation and catalytic aldol condensation of ketone with rhodium(III)-porphyrin perchlorate under neutral and mild conditions
Aoyama, Y.,Tanaka, Y.,Yoshida, T.,Toi, H.,Ogoshi, H.
, p. 251 - 266 (2007/10/02)
Acetone and methyl ethyl ketone undergo facile and direct metalation at the methyl groups by a cationic (octaethylporphyrinato) rhodium(III) complex with a non-coordinating perchlorate counteranion, (OEP)RhIII(ClO4), under mild conditions.Acetylacetone and ethyl acetoacetate are similarly metalated at the internal methylene groups.The metalation of acetone is first-order with respect to both rhodium complex and ketone, and involves the (OEP)RhIII(ClO4)-assisted, rate-determining enolization of the ketone.The resulting 2-oxopropyl-rhodium derivative undergoes facile cleavage of the C-Rh bond with electrophiles such as H(1+) and Br2.When cyclohexanone is used as substrate, on the other hand, (OEP)RhIII(ClO4) catalyzes the aldol condensation of the ketone effectively, where the intermediate cyclohexanone enolate reacts with the ketone or other carbonyl compound present and regenerates the RhIII complex.An essential aspect of the present reaction is the remarkable ability of (OEP)RhIII(ClO4) to promote enolization of simple ketones by activation with charge-separated III>+ (a Lewis acid) under mild and neutral conditions.The second-order rate constant of (OEP)RhIII(ClO4)-assisted enolization of acetone at 30 deg C (k2 = 2.6 * E-4 M-1 sec-1) is E7 times as large as that of its spontaneous enolization in water, where water is both acid and base.
Acetylation de trimethylsilyl bicyclo(n,1,0)alcanes : nouvelles syntheses de l'acetyl cyclohexene-2 et d'acetyl bicyclo(n,1,0)alcanes
Ahra, M.,Grignon-Dubois, M.
, p. 820 - 824 (2007/10/02)
Acetylation of trimethylsilyl bicyclo(n,1,0)alkanes was studied using the CH3COCl/AlCl3 complex.The results showed that both larger cycle size (n = 3, 4 or 6) and stereochemistry of the substrate (SiMe3 group in endo or exo position) played a prominent role in the orientation of the reaction : depending upon the starting products, either bicyclic or ethylenic and/or chloro ketones were formed.The results can be rationalized in terms of steric hindrance considerations.They allowed us to propose a new convenient synthesis of acetyl bicyclo(n,1,0)alkanes and also of 1-acetyl 2-cyclohexene.
