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Synthesis 2012(4): 513-526  
DOI: 10.1055/s-0031-1289679
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Bicyclo[3.2.0]heptane-Based Enamides by Ru/PNNP-Catalyzed Enantioselective Ficini Reactions: Scope and Application in Ligand Design

Christoph Schotes, Raphael Bigler, Antonio Mezzetti*
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Fax: +41(44)6321310; e-Mail: mezzetti@inorg.chem.ethz.ch;
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Publication History

Received 9 December 2011
Publication Date:
30 January 2012 (online)

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Abstract

Double chloride abstraction from [RuCl2(PNNP)] [PNNP­ = (S,S)-N,N′-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine] gives the elusive dicationic adduct [Ru(OEt)2(PNNP)]²+ which catalyzes the [2+2] cycloaddition of cyclic alkylidene β-keto esters with a variety of ynamides to produce bicyclo[3.2.0]heptane-based enamides with high yields and enan­tioselectivity. The structural features of these products are discussed and selected examples are converted into highly modular diene, phosphite-alkene, and diphosphite derivatives, which were tested as bidentate ligands with Rh(I), Ir(I), and Pd(II).

Key words

asymmetric catalysis - biaryls - cycloaddition - bicyclic compounds - ligands - phosphorus - ruthenium

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15

Also, an attempted acetal protection of 5a under various standard conditions failed, most probably due to the congested spatial arrangement.

23

Nucleophilic substitution reactions on Ph2PCl with 6a and Et3N or NaH as a base were attempted. However, no conversion was detected by TLC and, after aqueous workup, by NMR after 24 h at r.t.

26

X-ray crystallography: CCDC-856610 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; or
e-mail: deposit@ccdc.cam.ac.uk]. Although the starting Ficini product 5p was enantiomerically enriched (74% ee), 8d crystallized from hot hexane as a racemate in the centrosymmetric P21/c space group. See the Supporting Information for selected distances and angles.

28

See Supporting Information for additional studies with ligand 10b and [Rh(acac)(C2H4)2] as metal precursor.