Synthesis 2016; 48(08): 1117-1121
DOI: 10.1055/s-0035-1560410
psp
© Georg Thieme Verlag Stuttgart · New York

Optimized Syntheses of Optically Pure P-Alkene Ligands: Crystal Structures of a Pair of P-Stereogenic Diastereomers

Alberto Herreraa, Anthony Lindenb, Frank W. Heinemanna, René-Chris Brachvogela, Max von Deliusa, Romano Dorta*a
  • aDepartment Chemie und Pharmazie, Friedrich–Alexander–Universität Erlangen–Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany   Email: romano.dorta@fau.de
  • bInstitut für Chemie, Universität Zürich, Winterthurerstrasse 190, 8057, Zurich, Switzerland
Further Information

Publication History

Received: 19 January 2016

Accepted after revision: 26 January 2016

Publication Date:
17 February 2016 (eFirst)

Abstract

The ‘privileged’ P-alkene ligand (S)-2 is synthesized on a > 40 gram scale in 96% yield starting from dibenz[b,f]azepine-PCl2 (1; accessible on > 80 g scale) and (S)-BINOL. Similarly, the P-alkenes (R)-3 and the ‘chiral-at-P’ (SP ,SC )-4 are obtained from (R)-Taddol [(R,R)-α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanol] and (S)-α,α-diphenylprolinol, respectively, in multigram quantities and high purity. The crystal structures of (SP ,SC )-4, its diastereomer (RP ,SC )-4, and of the (R)-SPINOL-derived ligand (R)-5 are reported. A slightly revised synthesis of SPINOL is also disclosed.

Supporting Information