0000000000352091
AUTHOR
Stephanie Toulot
A Straightforward Route to Homoallyl-Homocrotylamines Promoted by a Titanium Complex
I�-Allyltitanium complexes, generated in situ from 1,3-dienes and Cp2TiH, react with benzotriazole derivatives to give homoallylic amines in good yields. Under similar conditions, triple cascade reactions (allyltitanation followed by cationic 2-aza-Cope rearrangement followed by a second allyltitanation) occur from bis(benzotriazolyl) compounds affording a straightforward route to homoallyl-(E)-homocrotylamines. A theoretical study provides further insight into the factors that govern the selectivity of this sequence of reactions. The titanium-promoted reductive coupling of 1,3-dienes with bis(benzotriazolyl) compounds as substrates led selectively to homoallyl-homocrotylamines through a tr…
ChemInform Abstract: A Straightforward Route to Homoallyl-Homocrotylamines Promoted by a Titanium Complex.
This publication also contains theoretical studies and calculations concerning the reaction.
Titanium complexes for the formation of nitrogen compounds : synthesis of homoallylamines and amidines
Homoallylic amines are key reagents for the formation of a large number of biologically interesting products. Due to the double bond of their allylic moiety, easily functionalisable, they are commonly used in organic synthesis. This research work deals with the synthesis of homoallylic amines thanks to titanium complexes. In fact, the reductive coupling between of imines and dienes promoted by titanium allows the formation of diastereoisomeric homoallylamines syn and anti. The diastereoselectivity of the reaction is directly affected by the nitrogen substituent. Whether it is benzyl or phenyl, the selectivity will be in favour of syn or anti respectively. Moreover, the addition of a the Lew…
Development of Bimetallic Titanocene−Ruthenium−Arene Complexes As Anticancer Agents: Relationships between Structural and Biological Properties
A series of bimetallic titanium-ruthenium complexes of general formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CR(2))(n)PR'R'')TiCl(2)](η(6)-p-cymene)RuCl(2) (n = 0, 1, 2 or 4; R = H or Me; R' = H, Ph, or Cy; R'' = Ph or Cy) have been synthesized, including two novel compounds as well as two cationic derivatives of formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)] [(η(6)-p-cymene)RuCl](BF(4)) (n = 0 or 2). The solid state structure of two of these compounds was also established by X-ray crystallography. The complexes showed a cytotoxic effect on human ovarian cancer cells and were markedly more active than their Ti or Ru monometallic analogues titanocene dichloride and RA…