Enantioselective ficini reaction: Ruthenium/PNNP-catalyzed [2+2] cycloaddition of ynamides with cyclic enones

Angewandte Chemie - International Edition

Volumn 50, Issue 13, 2011, Pages 3072-3074

  Schotes, Christoph ^a   Mezzetti, Antonio ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

Alkynes; Asymmetric catalysis; Cycloaddition; Ficini reaction; Ruthenium

Indexed keywords

[2 + 2] CYCLOADDITION; ALKYNES; ASYMMETRIC CATALYSIS; CHEMICAL EQUATIONS; CHLORIDE ABSTRACTION; COMPLEX 1; ENANTIOSELECTIVE; FICINI REACTION; HIGH YIELD; KETO ESTER;

ACETYLENE; CHLORINE COMPOUNDS; ENANTIOSELECTIVITY; ESTERS; RUTHENIUM;

CATALYSIS;

AMIDE; KETONE; ORGANOMETALLIC COMPOUND; RUTHENIUM;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; STEREOISOMERISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

AMIDES; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; KETONES; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; RUTHENIUM; STEREOISOMERISM;

EID: 79952662125     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201007753     Document Type: Article

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24. The value of the Flack parameter in dicates that the absolute configuration is 1R,5S. This assignment has been confirmed by reduction of the carbonyl function of 5a and esterification of the resulting alcohol with (-)-camphanic acid chloride to give 6. See the Supporting Information for synthetic details and X-ray structures. CCDC 802191 (6) and 802192 (5a) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
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26. The transition state (TS) in Figure 2 has been modeled starting from the X-ray data of 3 and imposing a bond length of 2.0 Å between the C1 atom of the ynamide and C3 atom of the enone. Interestingly, a C1′-C2′-C3- C2 torsion angle of 0° is obtained for the TS without imposing any additional constraint. See the Supporting Information for the details of MM calculations.