Cationic palladium(ii)-catalyzed dehydrative nucleophilic substitutions of benzhydryl alcohols with electron-deficient benzenethiols in water

2016 ◽  
Vol 14 (29) ◽  
pp. 7038-7045 ◽  
Author(s):  
Hidemasa Hikawa ◽  
Yumo Machino ◽  
Mariko Toyomoto ◽  
Shoko Kikkawa ◽  
Isao Azumaya
Keyword(s):  
Nucleophilic Substitution ◽  
Lewis Acids ◽  
Nucleophilic Substitutions ◽  
Cationic Palladium

An efficient direct nucleophilic substitution of benzhydryl alcohols with electron-deficient benzenethiols using cationic Pd(ii) catalysts as Lewis acids in water is reported.

Organic Reactivity in Ionic Liquids: Some Mechanistic Insights into Nucleophilic Substitution Reactions

2005 ◽  
Vol 2005 (7) ◽  
pp. 413-417 ◽  
Author(s):  
N. Llewellyn Lancaster
Keyword(s):  
Ionic Liquids ◽  
Nucleophilic Substitution ◽  
Organic Reactions ◽  
Substitution Reactions ◽  
Nucleophilic Substitutions ◽  
Nucleophilic Substitution Reactions ◽  
Quantitative Studies ◽  
Alternative Solvents ◽  
Molecular Solvents ◽  
Organic Reactivity

Ionic liquids have been advanced as alternative solvents for organic reactions. In this paper, the principal findings of studies on nucleophilic substitutions in ionic liquids are reviewed. Thus our examination of halides (Cl-, Br- and I) in a range of ionic liquids is combined with our study of amine nucleophilicity into a single narrative. There have been a few other quantitative studies of nucleophilic substitutions in ionic liquids, and the results of these studies are also summarised in this work. These data are compared to related reactions in molecular solvents, and used to show where ionic liquids do (and do not) offer advantages over molecular solvents for nucleophilic substitutions.

Synthesis of aromatic functionalized cage-rearranged silsesquioxanes (T8, T10, and T12) via nucleophilic substitution reactions

2015 ◽  
Vol 44 (3) ◽  
pp. 916-919 ◽  
Author(s):  
Supansa Chimjarn ◽  
Rungthip Kunthom ◽  
Prapassorn Chancharone ◽  
Rapheepraew Sodkhomkhum ◽  
Preeyanuch Sangtrirutnugul ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Building Blocks ◽  
Polyhedral Oligomeric Silsesquioxanes ◽  
Substitution Reactions ◽  
Nucleophilic Substitutions ◽  
Inorganic Hybrid ◽  
Nucleophilic Substitution Reactions

Organic–inorganic hybrid nano-building blocks of aryl nitro-, aldehyde-, and bromo-functionalized polyhedral oligomeric silsesquioxanes (T8, T10, and T12) were easily prepared through nucleophilic substitutions.

scholarly journals The Reaction of Hydrogen Halides with Tetrahydroborate Anion and Hexahydro-Closo-Hexaborate Dianion

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3754
Author(s):  
Igor E. Golub ◽  
Oleg A. Filippov ◽  
Natalia V. Belkova ◽  
Lina M. Epstein ◽  
Elena S. Shubina
Keyword(s):  
Dft Calculations ◽  
Nucleophilic Substitution ◽  
Solvent Effects ◽  
Lewis Acids ◽  
Hydrogen Halides ◽  
Hydride Ion ◽  
Low Degree ◽  
Successive Substitution ◽  
Electron Deficiency ◽  
Ab Initio Dft

The mechanism of the consecutive halogenation of the tetrahydroborate anion [BH4]− by hydrogen halides (HX, X = F, Cl, Br) and hexahydro-closo-hexaborate dianion [B6H6]2− by HCl via electrophile-induced nucleophilic substitution (EINS) was established by ab initio DFT calculations [M06/6-311++G(d,p) and wB97XD/6-311++G(d,p)] in acetonitrile (MeCN), taking into account non-specific solvent effects (SMD model). Successive substitution of H− by X− resulted in increased electron deficiency of borohydrides and changes in the character of boron atoms from nucleophilic to highly electrophilic. This, in turn, increased the tendency of the B–H bond to transfer a proton rather than a hydride ion. Thus, the regularities established suggested that it should be possible to carry out halogenation more selectively with the targeted synthesis of halogen derivatives with a low degree of substitution, by stabilization of H2 complex, or by carrying out a nucleophilic substitution of B–H bonds activated by interaction with Lewis acids (BL3).

Direct Nucleophilic Substitution of Alcohols by Brønsted or Lewis Acids Activation: An Update

2021 ◽  
pp. 123-154
Author(s):  
Pier Giorgio Cozzi ◽  
Andrea Gualandi ◽  
Luca Mengozzi ◽  
Elisabetta Manoni ◽  
Claire Margaret Wilson
Keyword(s):  
Nucleophilic Substitution ◽  
Lewis Acids

Stereochemistry of electrophilic and nucleophilic substitutions at phosphorus

2019 ◽  
Vol 91 (1) ◽  
pp. 43-57 ◽  
Author(s):  
Oleg I. Kolodiazhnyi
Keyword(s):  
Nucleophilic Substitution ◽  
Absolute Configuration ◽  
Electrophilic Substitution ◽  
Thermodynamic Control ◽  
Nucleophilic Substitutions ◽  
Electrophilic Substitutions ◽  
Organophosphorus Chemistry

Abstract Nucleophilic and electrophilic substitutions are the most often applied reactions in organophosphorus chemistry. They are closely interrelated, because in a reacting pair always one reagent is an electrophile, and another nucleophile. The reactions of electrophilic and nucleophilic substitutions at the phosphorus center proceed via the formation of a pentacoordinated intermediate. The mechanism of nucleophilic substitution involves the exchange of ligands in the pentacoordinate phosphorane intermediate, leading to the more stable stereomer under the thermodynamic control. Electrophilic substitution proceeds with retention of absolute configuration, whereas nucleophilic substitution with inversion of configuration at the phosphorus center.

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