Regioselective Carbon-Carbon Bond Formation in Titanium Mediated Reaction of Ethylmagnesium Bromide with Allylic Alcohols and Allylic Ethers

Synlett ◽  
2001 ◽  
Vol 2001 (01) ◽  
pp. 0049-0052 ◽  
Author(s):  
Oleg G. Kulinkovich ◽  
Oleg L. Epstein ◽  
Vladimir E. Isakov ◽  
Ekaterina A. Khmel'nitskaya
Keyword(s):  
Bond Formation ◽  
Allylic Alcohols ◽  
Ethylmagnesium Bromide ◽  
Carbon Bond ◽  
Carbon Carbon Bond ◽  
Allylic Ethers

Titanacyclopropanes as versatile intermediates for carbon-carbon bond formation in reactions with unsaturated compounds

2000 ◽  
Vol 72 (9) ◽  
pp. 1715-1719 ◽  
Author(s):  
O. G. Kulinkovich
Keyword(s):  
Reaction Mechanism ◽  
Bond Formation ◽  
Grignard Reagents ◽  
Allylic Alcohols ◽  
Ethylmagnesium Bromide ◽  
Carbon Bond ◽  
Unsaturated Compounds ◽  
Carbon Carbon Bond ◽  
Reaction Proceeds

Dialkoxytitanacyclopropane intermediates [or titanium (II)-olefin complexes] generated in situ from ethylmagnesium bromide and titanium (IV) isopropoxide react with allylic alcohols and allylic ethers to afford SN2' allylic ethylation products. The reaction proceeds with high regioselectivity and with low to high trans-/cis-stereoselectivity. This observation and others suggest a reaction mechanism involving an EtMgBr-initiated formation of titanacyclopentane ate complex 10 from titanacyclopropane-olefin complex 7 as a key step. Based on this assumption, a modified mechanism of titanium-mediated cyclopropanation of esters with Grignard reagents is proposed.

Carbon-Carbon Bond Formation: Palladium-Catalyzed Oxidative Cross-Coupling of N-Tosylhydrazones with Allylic Alcohols

2012 ◽  
Vol 18 (34) ◽  
pp. 10497-10500 ◽  
Author(s):  
Huoji Chen ◽  
Li Huang ◽  
Wei Fu ◽  
Xiaohang Liu ◽  
Huanfeng Jiang
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Allylic Alcohols ◽  
Carbon Bond ◽  
Carbon Carbon Bond ◽  
Palladium Catalyzed

Carbon–carbon bond formation in the dichlorobis(triphenylphosphine)nickel-catalysed reaction between Grignard reagents and allylic alcohols

1968 ◽  
Vol 0 (24) ◽  
pp. 1604-1605 ◽  
Author(s):  
Claude Chuit ◽  
Hugh Felkin ◽  
Claude Frajerman ◽  
Georges Roussi ◽  
Gérard Swierczewski
Keyword(s):  
Bond Formation ◽  
Grignard Reagents ◽  
Allylic Alcohols ◽  
Carbon Bond ◽  
Catalysed Reaction ◽  
Carbon Carbon Bond

Carbon Dioxide-Mediated C(sp2)–H Arylation of Primary and Secondary Benzylamines

2018 ◽  
Author(s):  
Mohit Kapoor ◽  
Pratibha Chand-Thakuri ◽  
Michael Young
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Carbon Bond ◽  
Chelate Effect ◽  
Free Amine ◽  
Carbon Carbon Bond ◽  
New Strategy ◽  
Metal Catalyzed

Carbon-carbon bond formation by transition metal-catalyzed C–H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of <i>ortho</i>-arylbenzylamines, however, effective <i>ortho</i>-C–C bond formation from C–H bond activation of free primary and secondary benzylamines using Pd<sup>II</sup> remains an outstanding challenge. Presented herein is a new strategy for constructing <i>ortho</i>-arylated primary and secondary benzylamines mediated by carbon dioxide (CO<sub>2</sub>). The use of CO<sub>2</sub> is critical to allowing this transformation to proceed under milder conditions than previously reported, and that are necessary to furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, a chelate effect is demonstrated to facilitate selective monoarylation.

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