Rapid Injection NMR Reveals η3 ‘π-Allyl’ CuIII Intermediates in Addition Reactions of Organocuprate Reagents

2012 ◽  
Vol 134 (23) ◽  
pp. 9557-9560 ◽  
Author(s):  
Steven H. Bertz ◽  
Richard A. Hardin ◽  
Michael D. Murphy ◽  
Craig A. Ogle ◽  
Joshua D. Richter ◽  
...  
Keyword(s):  
Addition Reactions ◽  
Rapid Injection ◽  
Organocuprate Reagents

On the Mechanism of Lewis Base Catalyzed Aldol Addition Reactions: Kinetic and Spectroscopic Investigations Using Rapid-Injection NMR

2009 ◽  
Vol 131 (33) ◽  
pp. 11770-11787 ◽  
Author(s):  
Scott E. Denmark ◽  
Brian M. Eklov ◽  
Peter J. Yao ◽  
Martin D. Eastgate
Keyword(s):  
Lewis Base ◽  
Addition Reactions ◽  
Spectroscopic Investigations ◽  
Rapid Injection ◽  
Aldol Addition

Conjugate addition reactions of .alpha.,.beta.-unsaturated ketones with higher order, mixed organocuprate reagents, R2Cu(CN)Li2

1984 ◽  
Vol 49 (21) ◽  
pp. 3938-3942 ◽  
Author(s):  
Bruce H. Lipshutz ◽  
Robert S. Wilhelm ◽  
Joseph A. Kozlowski
Keyword(s):  
Conjugate Addition ◽  
Higher Order ◽  
Addition Reactions ◽  
Unsaturated Ketones ◽  
Alpha Beta ◽  
Organocuprate Reagents

Thia-Michael Addition Reactions in Water Using 3-[Bis(Alkylthio) Methylene] Pentane-2,4-Diones as Odorless and Efficient Thiol Equivalents

2007 ◽  
Vol 4 (4) ◽  
pp. 281-284 ◽  
Author(s):  
Yanyan Chai ◽  
Dewen Dong ◽  
Yan Ouyang ◽  
Yongjiu Liang ◽  
Yan Wang ◽  
...  
Keyword(s):  
Michael Addition ◽  
Addition Reactions

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

Relative Reactivities of 1,1,1-Trichloroethane and 1,1,1-Trichlorotrifluoroethane in Competitive Addition Reactions

1992 ◽  
Vol 57 (6) ◽  
pp. 1291-1298 ◽  
Author(s):  
František Adámek ◽  
Milan Hájek ◽  
Zbyněk Janoušek
Keyword(s):  
Free Radical ◽  
Reaction Mechanism ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Radical Initiation ◽  
Amine Complexes ◽  
Free Radical Initiation ◽  
Ru Complexes ◽  
Radical Initiators

Relative reactivity of CH3CCl3 and CF3CCl3 measured in competitive addition reactions with 1-hexene in the presence of free radical initiators or Cu, Pd and Ru complexes was found to depend on the type of catalyst. The unusual course of the reaction has been found in the additions catalyzed with copper(I)-amine complexes where CH3CCl3 in competition with CF3CCl3 was completely unreactive. The results have been explained in terms of the change of reaction mechanism and compared with classical free radical initiation.

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