10.1021/om060234c.s003
Yutaka Matsuo
Yutaka
Matsuo
Yuichi Mitani
Yuichi
Mitani
Yu-Wu Zhong
Yu-Wu
Zhong
Eiichi Nakamura
Eiichi
Nakamura
Remote Chirality Transfer within a Coordination Sphere by the Use
of a Ligand Possessing a Concave Cavity
American Chemical Society
2006
propho
Concave Cavity
chiral element
Coordination Sphere
diastereoselectivity
Remote Chirality Transfer
metal coordination sphere
cationic complexes
Ligand Possessing
metal ligand
NC
CO
t BuCN
Cl
Ru
chirality transfer
2006-05-22 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Remote_Chirality_Transfer_within_a_Coordination_Sphere_by_the_Use_of_a_Ligand_Possessing_a_Concave_Cavity/3221587
The possibility to enhance the effect of a modest chiral element in a metal ligand by the use of a
second ligand possessing a concave cavity has been examined for the examples of 1,3- and 1,4-chirality
transfer within the metal coordination sphere. Complexation of Ru(C<sub>60</sub>Me<sub>5</sub>)Cl(CO)<sub>2</sub> with (<i>R</i>)-prophos
[(<i>R</i>)-1,2-bis(diphenylphosphino)propane] took place with excellent diastereoselectivity to give a
configurationally stable chiral-at-metal complex, Ru(C<sub>60</sub>Me<sub>5</sub>)Cl((<i>R</i>)-prophos). This complex was converted,
with good to perfect diastereoselectivity, into a variety of cationic complexes, [Ru(C<sub>60</sub>Me<sub>5</sub>)((<i>R</i>)-prophos)L][SbF<sub>6</sub>] (L = MeCN, <i><sup>t</sup></i><sup></sup>BuCN, methacrolein, acetone, CO, BnNC, 2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>NC), and a vinylidene
complex, [Ru(C<sub>60</sub>Me<sub>5</sub>)(CCPhH)((<i>R</i>)-prophos)][SbF<sub>6</sub>]. The chirality transfer to the reactants reacting
in the outer sphere of the coordination resulted in an asymmetric Diels−Alder reaction, albeit with modest
selectivity.