4-Homoadamantyl cation. II. Mechanistic studies on Lewis acid catalyzed conversion of homoadamantene to 2-methyladamantane by carbon-13 labeling techniques. Convenient synthesis of 4-homoadamantanone-5-13C and homoadamantene-4-13C

1975 ◽  
Vol 40 (25) ◽  
pp. 3772-3776 ◽  
Author(s):  
Katica Mlinaric-Majerski ◽  
Zdenko Majerski ◽  
Ernoe Pretsch
2012 ◽  
Vol 77 (22) ◽  
pp. 10184-10193 ◽  
Author(s):  
Luciana M. Ramos ◽  
Adrian Y. Ponce de Leon y Tobio ◽  
Marcelo R. dos Santos ◽  
Heibbe C. B. de Oliveira ◽  
Alexandre F. Gomes ◽  
...  

RSC Advances ◽  
2019 ◽  
Vol 9 (64) ◽  
pp. 37675-37685
Author(s):  
Pan Du ◽  
Jiyang Zhao

We investigated the mechanism of the dehydrosilylation of (hetero)arenes and extended the scope of the silylation catalysts and substrates.


Synthesis ◽  
1996 ◽  
Vol 1996 (01) ◽  
pp. 141-144 ◽  
Author(s):  
Holger Paulsen ◽  
Claudia Graeve ◽  
Dieter Hoppe

2018 ◽  
Author(s):  
Haley Albright ◽  
Paul S. Riehl ◽  
Christopher C. McAtee ◽  
Jolene P. Reid ◽  
Jacob R. Ludwig ◽  
...  

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in situ formation of a homobimetallic singly-bridged iron(III)-dimer as the active catalytic species. These “superelectrophiles” function as more powerful Lewis acid catalysts that form upon association of individual iron(III)-monomers. While this mode of Lewis acid activation has previously been postulated to exist, it has not yet been applied in a catalytic setting. The insights presented are expected to enable further advancement in Lewis acid catalysis by building upon the activation principle of “superelectrophiles” and broaden the current scope of catalytic carbonyl-olefin metathesis reactions.</div>


Author(s):  
Juha Siitonen ◽  
Padmanabha V. Kattamuri ◽  
Muhammed Yousufuddin ◽  
Laszlo Kurti

Unprotected keto- and aldoximes are readily <i>C</i>-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly-substituted <i>N</i>-alpha-secondary (2°) and tertiary (3°) hydroxylamines. The method’s synthetic utility is demonstrated with the total synthesis of the trace alkaloid <i>N</i>-methyl-euphococcine. Preliminary experimental and computational mechanistic studies point toward the formation of a boroxine as the active allylating species.<br>


Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1170
Author(s):  
Yuan Zhu ◽  
Benkun Qi ◽  
Xinquan Liang ◽  
Jianquan Luo ◽  
Yinhua Wan

Herein, corn stover (CS) was pretreated by less corrosive lewis acid FeCl3 acidified solutions of neat and aqueous deep eutectic solvent (DES), aqueous ChCl and glycerol at 120 °C for 4 h with single FeCl3 pretreatment as control. It was unexpected that acidified solutions of both ChCl and glycerol were found to be more efficient at removing lignin and xylan, leading to higher enzymatic digestibility of pretreated CS than acidified DES. Comparatively, acidified ChCl solution exhibited better pretreatment performance than acidified glycerol solution. In addition, 20 wt% water in DES dramatically reduced the capability of DES for delignification and xylan removal and subsequent enzymatic cellulose saccharification of pretreated CS. Correlation analysis showed that enzymatic saccharification of pretreated CS was highly correlated to delignification and cellulose crystallinity, but lowly correlated to xylan removal. Recyclability experiments of different acidified pretreatment solutions showed progressive decrease in the pretreatment performance with increasing recycling runs. After four cycles, the smallest decrease in enzymatic cellulose conversion (22.07%) was observed from acidified neat DES pretreatment, while the largest decrease (43.80%) was from acidified ChCl pretreatment. Those findings would provide useful information for biomass processing with ChCl, glycerol and ChCl-glycerol DES.


Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 1 ◽  
Author(s):  
Jie Zhang ◽  
Zhiming Zhang ◽  
Fulin Yang ◽  
Haoke Zhang ◽  
Jingzhi Sun ◽  
...  

Novel polymerizations based on alkyne monomers are becoming a powerful tool to construct polymers with unique structures and advanced functions in the areas of polymer and material sciences, and scientists have been attracted to develop a variety of novel polymerizations in recent decades. Therein, catalytic systems play an indispensable role in the influence of polymerization efficiencies and the performances of the resultant polymers. Concerning the shortcomings of metallic catalysts, much of the recent research focus has been on metal-free polymerization systems. In this paper, metal-free catalysts are classified and the corresponding polymerizations are reviewed, including organobase-catalyzed polymerizations, Lewis-acid-catalyzed polymerizations, as well as catalyst-free polymerizations. Moreover, the challenges and perspectives in this area are also briefly discussed.


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