Non-bonding 1,5-S···O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles† †Electronic supplementary information (ESI) available: 1H and 13C{1H} NMR spectra and HPLC traces of all novel compounds. Coordinates, thermal corrections, and energies of all computed structures. See DOI: 10.1039/c6sc00940a Click here for additional data file. Click here for additional data file.

نویسندگان

  • Emily R. T. Robinson
  • Daniel M. Walden
  • Charlene Fallan
  • Mark D. Greenhalgh
  • Paul Ha-Yeon Cheong
  • Andrew D. Smith
چکیده

Isothiourea-catalyzed annulations between 2-acyl benzazoles and a,b-unsaturated acyl ammonium intermediates are selectively tuned to form either lactam or lactone heterocycles in good yields (up to 95%) and high ee (up to 99%) using benzothiazole or benzoxazole derivatives, respectively. Computation gives insight into the significant role of two 1,5-S/O interactions in controlling the structural preorganization and chemoselectivity observed within the lactam synthesis with benzothiazoles as nucleophiles. When using benzazoles the absence of a second stabilizing non-bonding 1,5-S/O interaction leads to a dominant C–H/O interaction in determining structural preorganization and lactone formation.

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منابع مشابه

6-exo-trig Michael addition-lactonizations for catalytic enantioselective chromenone synthesis† †Electronic supplementary information (ESI) available: Experimental procedures; characterization data for novel compounds; 1H and 13C NMR spectra, HPLC traces,12 and X-ray crystallographic data files compounds 9 and 27 (CIF). CCDC 1510311 and 1510312. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6cc10178j Click here for additional data file. Click here for additional data file.

The catalytic enantioselective 6-exo-trig Michael addition-lactonization of enone-acid substrates to form cis-chromenones with high diastereo- and enantiocontrol was developed using the commercially available isothiourea tetramisole. An acidic workup proved necessary to minimize product epimerization and maximize product er, providing cis-chromenones in excellent yield, and with excellent diast...

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Stereodivergent, Diels–Alder-initiated organocascades employing α,β-unsaturated acylammonium salts: scope, mechanism, and application† †Electronic supplementary information (ESI) available: Experimental procedures and characterization details for all new compounds including 1H and 13C NMR spectra, computational data, crystallographic data, chiral phase-HPLC traces. CCDC 972246. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc04273b Click here for additional data file. Click here for additional data file.

Chiral a,b-unsaturated acylammonium salts are novel dienophiles enabling enantioselective Diels–Alderlactonization (DAL) organocascades leading to cisand trans-fused, bicyclic gand d-lactones from readily prepared dienes, commodity acid chlorides, and a chiral isothiourea organocatalyst under mild conditions. We describe extensions of stereodivergent DAL organocascades to other racemic dienes b...

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عنوان ژورنال:

دوره 7  شماره 

صفحات  -

تاریخ انتشار 2016