Enantiopure planar chiral and chiral-at-metal iridacycles derived from bulky cobalt sandwich complexes

Ross A. Arthurs, Christopher C. Prior, David L. Hughes, Vasily S. Oganesyan, Christopher J. Richards

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)
5 Downloads (Pure)

Abstract

Reaction of (η5-(S)-2-(4-methylethyl)oxazolinylcyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt with [IrCp*Cl2]2 in acetonitrile with KPF6 and KOt-Bu resulted in S,Sp,SIr and S,Rp,RIr configured acetonitrile and Cp* coordinated cationic iridacycles (d.r. up to 4.8 : 1 – kinetic control), the planar chiral configuration dictating the configuration of the pseudo-tetrahedral iridium-based stereogenic centre. Addition of water to the cycloiridation reaction resulted in an increase in yield (up to 78%) at the cost of diastereoselectivity. Use of the corresponding substrate containing a t-Bu rather than an i-Pr substituted oxazoline gave exclusively the S,Sp,SIr diastereoisomer, and under the same conditions (S)-2-ferrocenyl- 4-(1,1-dimethylethyl)oxazoline cycloiridated to give only the S,Sp,SIr diastereoisomer. Substitution reactions of the title complexes at iridium proceeded with retention of configuration, a computational study revealing the proposed coordinatively unsaturated intermediate of a dissociative mechanism to display a relatively weak Co-Ir interaction, and a pronounced steric effect as the basis of stereocontrol.
Original languageEnglish
Pages (from-to)4204-4212
Number of pages9
JournalOrganometallics
Volume37
Issue number22
Early online date12 Nov 2018
DOIs
Publication statusPublished - 26 Nov 2018

Cite this