Rhodium(I)-catalyzed [2+2+2] cycloadditions with N-functionalized 1- alkynylamides: A conceptually new strategy for the regiospecific synthesis of substituted indolines

Angewandte Chemie - International Edition

Volumn 38, Issue 16, 1999, Pages 2426-2430

  Witulski, Bernhard ^a   Stengel, Thomas ^a  

^a D 67663   (Germany)

Author keywords

Alkynes; Cyclotrimerizations; Homogeneous catalysis; Indolines; Rhodium

Indexed keywords

AMIDE; INDOLE DERIVATIVE; RHODIUM;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CYCLIZATION; DRUG STRUCTURE; DRUG SYNTHESIS; STEREOCHEMISTRY; STEREOSPECIFICITY;

EID: 0033549728     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990816)38:16<2426::AID-ANIE2426>3.0.CO;2-Y     Document Type: Article

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37. 13C NMR, IR spectroscopy, mass spectrometry, C,H,N analysis, and/or high-resolution mass spectrometry.
38. [10]g However, in the examples studied by us, cyclotrimerizations occurred in toluene, which may be due to an enhanced reactivity of the N-1-alkynylamides for cyclotrimerizations in comparison with that of the diynes studied by Grigg.
39. Additional monosubstituted alkynes, such as phenyl acetylene and 1-pentyne, undergo cyclotrimerization reactions with the diynes 4a, 3i, and 3j. Further studies are in progress to explore the mechanistic factors responsible for the selectivity, as well as cyclotrimerization studies with nickel and cobalt catalysts.
40. The structural assignment of compound 12a is based on 2D-NMR experiments (H, H-and C, H-COSY, as well as HMBC) and distinct NOE relationships. We would like to thank Prof. Dr. L Ernst (Technische Universität Braunschweig) for the NOE measurements.