scholarly journals Direct C(sp3)-H allylation of 2-alkylpyridines with Morita-Baylis-Hillman carbonates via a tandem nucleophilic substitution/aza-Cope rearrangement

2021 ◽  
Author(s):  
Siyu Wang ◽  
Lianyou Zheng ◽  
Shutao Wang ◽  
Shulin Ning ◽  
Zhuoqi Zhang ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Cope Rearrangement ◽  
Allylic Alkylation ◽  
Catalyst Free ◽  
Simple Strategy ◽  
Plausible Mechanism ◽  
Mechanism Of The Reaction

A base- and catalyst-free C(sp3) – H allylic alkylation of 2-alkylpyridines with Morita-Baylis-Hillman (MBH) carbonates was described. A plausible mechanism of the reaction might involve a tandem SN2’ type nucleophilic substitution followed by an aza-Cope rearrangement. Various alkyl substituents on 2-alkylpyridines were tolerated in the reaction to give the allylation products in 26-91% yields. The developed method provides a straightforward and operational simple strategy for the allylic functionalization of 2-alkypyridine derivatives.

scholarly journals Direct C(sp3)–H allylation of 2-alkylpyridines with Morita–Baylis–Hillman carbonates via a tandem nucleophilic substitution/aza-Cope rearrangement

2021 ◽  
Vol 17 ◽  
pp. 2505-2510
Author(s):  
Siyu Wang ◽  
Lianyou Zheng ◽  
Shutao Wang ◽  
Shulin Ning ◽  
Zhuoqi Zhang ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Cope Rearrangement ◽  
Allylic Alkylation ◽  
Catalyst Free ◽  
Simple Strategy ◽  
Plausible Mechanism ◽  
Mechanism Of The Reaction

A base- and catalyst-free C(sp3)–H allylic alkylation of 2-alkylpyridines with Morita–Baylis–Hillman (MBH) carbonates is described. A plausible mechanism of the reaction might involve a tandem SN2’ type nucleophilic substitution followed by an aza-Cope rearrangement. Various alkyl substituents on 2-alkylpyridines were tolerated in the reaction to give the allylation products in 26–91% yields. The developed method provides a straightforward and operational simple strategy for the allylic functionalization of 2-alkypyridine derivatives.

Pentacarbonylmanganese enolate and dienolate complexes. Preparative and mechanistic considerations

1990 ◽  
Vol 68 (3) ◽  
pp. 492-501 ◽  
Author(s):  
Andrew P. Masters ◽  
Ted S. Sorensen
Keyword(s):  
Nmr Spectroscopy ◽  
Nucleophilic Substitution ◽  
Reaction Products ◽  
Organic Products ◽  
Mechanism Of The Reaction ◽  
Model Reactions ◽  
Inorganic And Organic

Reactions of pentacarbonyl manganate anion with 4-halocrotonate esters or 2-halocarboxylate esters result in a complex set of inorganic and organic products, usually including the expected dienolate (or enolate) complexes. The reaction variables include the counterion, solvent, and halo group. The mechanism of the reaction has been investigated by conducting a thorough characterization of the reaction products under various conditions and also by carrying out model reactions. One can rationalize most of the non-organometallic products using either a radical or carbanion mechanism, but the latter seems to fit the available data better. Experimental procedures for optimizing the yield of the organometallic dienolate or enolate complexes have been worked out. Keywords: pentacarbonyl manganate, metalate nucleophilicity, enolate complex, nucleophilic substitution, 55Mn NMR spectroscopy.

Silica Chloride-Catalyzed One-Pot Isomerization - Chlorination, Arylation, and Etherification of Baylis - Hillman Adducts

2007 ◽  
Vol 60 (11) ◽  
pp. 850 ◽  
Author(s):  
Ponnusamy Shanmugam ◽  
Baby Viswambharan ◽  
Vadivel Vaithiyanathan
Keyword(s):  
Heterogeneous Catalyst ◽  
Thionyl Chloride ◽  
Good Yield ◽  
One Pot ◽  
Unsaturated Alcohols ◽  
Chloride Catalyst ◽  
Plausible Mechanism ◽  
Mechanism Of The Reaction

A convenient and efficient one-pot isomerization–chlorination, arylation, and etherification of several Baylis–Hillman adducts with silica chloride, an eco-friendly heterogeneous catalyst, silica chloride–arenes, and silica chloride–saturated and unsaturated alcohols as reagent systems are reported. These reactions furnished highly functionalized isomerized Baylis–Hillman derivatives in good yield. The efficiency and necessity of silica chloride catalyst was compared with thionyl chloride. A plausible mechanism of the reaction is proposed.

scholarly journals Water promoted allylic nucleophilic substitution reactions of (E)-1,3 diphenylallyl acetate

2018 ◽  
Vol 20 (2) ◽  
pp. 425-430 ◽  
Author(s):  
Seema A. Ghorpade ◽  
Dinesh N. Sawant ◽  
Arwa Makki ◽  
Nagaiyan Sekar ◽  
Jörg Eppinger
Keyword(s):  
Transition Metal ◽  
Nucleophilic Substitution ◽  
Allylic Alkylation ◽  
Substitution Reactions ◽  
Allylic Amination ◽  
Metal Free ◽  
Nucleophilic Substitution Reactions ◽  
Water Based

A transition metal free, reagent free, only water based, greener protocol for the allylic alkylation, allylic amination, and O-allylation of (E)-1,3-diphenylallyl acetate is described.

Transition-metal-free access to 2-aminopyridine derivatives from 2-fluoropyridine and acetamidine hydrochloride

2018 ◽  
Vol 16 (41) ◽  
pp. 7564-7567 ◽  
Author(s):  
Yibiao Li ◽  
Shuo Huang ◽  
Chunshu Liao ◽  
Yan Shao ◽  
Lu Chen
Keyword(s):  
Transition Metal ◽  
Nucleophilic Substitution ◽  
Efficient Method ◽  
Free Access ◽  
Metal Free ◽  
Catalyst Free ◽  
Hydrolysis Of

Under catalyst-free conditions, an efficient method for the synthesis of 2-aminopyridine derivatives through the nucleophilic substitution and hydrolysis of 2-fluoropyridine and acetamidine hydrochloride has been developed.

Catalyst-free and visible light promoted trifluoromethylation and perfluoroalkylation of uracils and cytosines

2018 ◽  
Vol 54 (97) ◽  
pp. 13662-13665 ◽  
Author(s):  
Yang Huang ◽  
Yun-Yun Lei ◽  
Liang Zhao ◽  
Jiwei Gu ◽  
Qiuli Yao ◽  
...  
Keyword(s):  
Visible Light ◽  
Catalyst Free ◽  
Simple Strategy

Here, we report a mild, catalyst-free and operationally simple strategy for the direct perfluoroalkylation of uracils, cytosines and pyridinones through a visible-light induced pathway.

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