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Enantioselective synthesis of isochromans and tetrahydroisoquinolines by C-H insertion of donor/donor carbenes.

  • Author(s): Nickerson, Leslie A
  • Bergstrom, Benjamin D
  • Gao, Mingchun
  • Shiue, Yuan-Shin
  • Laconsay, Croix J
  • Culberson, Matthew R
  • Knauss, Walker A
  • Fettinger, James C
  • Tantillo, Dean J
  • Shaw, Jared T
  • et al.
Abstract

Reports of C-H insertions forming six-membered rings containing heteroatoms are rare due to Stevens rearrangements occurring after nucleophilic attack on the carbene by a heteroatom. Using donor/donor carbenes and Rh2(R-PTAD)4 as a catalyst, we have synthesized a collection of isochroman substrates in good yield, with excellent diastereo- and enantioselectivity, and no rearrangement products were observed. Furthermore, we report the first synthesis of six-membered rings containing nitrogen by C-H insertion to form tetrahydroisoquinolines. In one case, a Stevens rearrangement product was isolated at elevated temperature from a carbamate-protected amine substrate and computational evidence suggests formation through a free ylide not bound to rhodium.

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