Sidechain Functionalizations by Cuprate Additions to Phosphorylallenyl-Substituted Arenetricarbonylchromium Complexes

• Published in: European journal of inorganic chemistry Vol. 1999; no. 2; pp. 225 - 233
• Main Authors: Ansorge, Markus, Polborn, Kurt, Müller, Thomas J. J.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 02.02.1999; WILEY‐VCH Verlag GmbH
• Subjects: Allenes; Arene complexes; Chromium; Cuprates; Sidechain functionalization
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/(SICI)1099-0682(19990202)1999:2<225::AID-EJIC225>3.0.CO;2-R

The cuprate addition to (arene)Cr(CO)3‐substituted phosphorylallenes 1 gives rise to the regioselective formation of complexed allylphosphane oxide derivatives 3a–c and allylphosphonate derivatives 3d–j in good yields. In the case of racemic planar chiral ortho‐substituted complexed (arylallenyl)phosphonates 1c, d the protonation of the intermediate allyl anion proceeds diastereoselectively due to the hindered rotation around the Cipso–Cα bond. This diastereoselective protonation is discussed on the basis of the conformational analysis as deduced from the X‐ray structure analyses of the allenylphosphonate 1d and the allylphosphonates 3i, j.