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Arthurs, Ross A., Hughes, David L. and Richards, Christopher J. 
ORCID: https://orcid.org/0000-0001-7899-4082
(2019)
Ferrocenyloxazoline-derived planar chiral palladacycles: C–H activation, transmetalation, and reversal of diastereoselectivity.
Organometallics, 38 (21).
pp. 4271-4279.
ISSN 0276-7333
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Abstract
Reinvestigation of the palladation of (S)-2-ferrocenyl-4-(methylethyl)oxazoline with Pd(OAc)2 in CH2Cl2 was found to proceed with a dr of 3.6:1 in favor of the resulting S,Sp palladacycle. A similar 4:1 dr was obtained using Na2PdCl4 in MeOH. As an alternative approach, highly diastereoselective lithiation (dr >100:1) and transmetalation were investigated. Addition of PdX2(COD) (X = Cl, Br) to (S,Rp)-2-lithio-1-(2′-(4′-methylethyl)oxazolinyl)ferrocene resulted in double halide substitution and formation of cis-(S,S,Sp,Sp)-bis[2-(2′-(4′-methylethyl)oxazolinyl)ferrocene-1-C,3′-N]palladium(II) (42% from X = Cl, 50% from X = Br). Selective monoprotodepalladation with HCl gave an S,Sp palladacycle containing a removable ferrocenyloxazoline ligand. Addition of PdCl2(MeCN)2 to mercuracycles in acetonitrile, themselves generated from Li–Hg transmetalation, followed by a brine wash gave (S,Sp)-di-μ-chlorobis[2-(2′-(4′-methylethyl)oxazolinyl)ferrocene-1-C,3′-N]dipalladium(II) as a single diastereoisomer in high yield. The alternative S,Rp diastereoisomer was obtained in the same way by use of a deuterium blocking group to reverse lithiation diastereoselectivity.
| Item Type: | Article |
|---|---|
| Faculty \ School: | Faculty of Science > School of Chemistry |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 27 Nov 2019 02:01 |
| Last Modified: | 22 Oct 2022 05:29 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/73120 |
| DOI: | 10.1021/acs.organomet.9b00551 |
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