13992-93-3Relevant 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
supporting information, 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.
Total Synthesis of (+/-)-Nitramine. Development of a Ketene Equivalent in the Ene Reaction
Snider, Barry B.,Cartaya-Marin, Claudia P.
, p. 1688 - 1691 (2007/10/02)
(+/-)-Nitramine (1a) was synthesized in seven steps from methylenecyclohexane in 33percent overall yield.A three-step sequence was developed from methylenecyclohexane to aldehyde 4 in which methyl α-chloroacrylate was used as a ketene equivalent in the ene reaction.Aldehyde 4 was converted to nitrone 3 which cyclized to a 2.5:1 mixture of 2 and 9.Hydrogenolysis of 2 gave 1a.Lewis acid catalyzed cyclization of 4 gave a 3.5:1 mixture of hydrindanones 13 and 14 at 25 deg C and a 12:1 mixture of 13 and 14 at -20 deg C.
