Synthesis of Benzodihydrofurans by Asymmetric C−H Insertion Reactions of Donor/Donor Rhodium Carbenes

Kellan N. Lamb, Richard A. Squitieri, Srinivasa R. Chintala, Ada J. Kwong, Edward I. Balmond, Cristian Soldi, Olga Dmitrenko, Marta Castiñeira Reis, Ryan Chung, J. Bennett Addison, James C. Fettinger, Jason E. Hein, Dean J. Tantillo, Joseph M. Fox, Jared T. Shaw

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Metal carbenes appended with two electron-donating groups, known as “donor/donor” carbenes, undergo diastereo- and enantioselective rhodium-catalyzed C−H insertion reactions with ether substrates to form benzodihydrofurans. Unlike the reactions of metal carbenes with electron-withdrawing groups attached, the attenuated electrophilicity enables these reactions to be conducted in Lewis basic solvents (e.g., acetonitrile) and in the presence of water. The diazo precursors for these species are prepared in situ from hydrazone using a mild and chemoselective oxidant (MnO2). Although this sequence often can be performed in one-pot, control experiments have elucidated why a “two-pot” process is often more efficient. A thorough screening of achiral catalysts demonstrated that sterically encumbered catalysts are optimal for diastereoselective reactions. Although efficient insertion into allylic and propargylic C−H bonds is observed, competing dipolar cycloaddition processes are noted for some substrates. The full substrate scope of this useful method of benzodihydrofuran synthesis, mechanisms of side reactions, and computational support for the origins of stereoselectivity are described.

Original languageEnglish (US)
Pages (from-to)11843-11855
Number of pages13
JournalChemistry - A European Journal
Volume23
Issue number49
DOIs
StatePublished - Sep 4 2017

Fingerprint

Rhodium
Substrates
Metals
Stereoselectivity
Hydrazones
Catalysts
Cycloaddition
Electrons
Acetonitrile
Oxidants
Ether
Ethers
Screening
Water
carbene
Experiments

Keywords

  • carbenes
  • density functional calculations
  • furans
  • oxidation
  • rhodium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Lamb, K. N., Squitieri, R. A., Chintala, S. R., Kwong, A. J., Balmond, E. I., Soldi, C., ... Shaw, J. T. (2017). Synthesis of Benzodihydrofurans by Asymmetric C−H Insertion Reactions of Donor/Donor Rhodium Carbenes. Chemistry - A European Journal, 23(49), 11843-11855. https://doi.org/10.1002/chem.201701630

Synthesis of Benzodihydrofurans by Asymmetric C−H Insertion Reactions of Donor/Donor Rhodium Carbenes. / Lamb, Kellan N.; Squitieri, Richard A.; Chintala, Srinivasa R.; Kwong, Ada J.; Balmond, Edward I.; Soldi, Cristian; Dmitrenko, Olga; Castiñeira Reis, Marta; Chung, Ryan; Addison, J. Bennett; Fettinger, James C.; Hein, Jason E.; Tantillo, Dean J.; Fox, Joseph M.; Shaw, Jared T.

In: Chemistry - A European Journal, Vol. 23, No. 49, 04.09.2017, p. 11843-11855.

Research output: Contribution to journalArticle

Lamb, KN, Squitieri, RA, Chintala, SR, Kwong, AJ, Balmond, EI, Soldi, C, Dmitrenko, O, Castiñeira Reis, M, Chung, R, Addison, JB, Fettinger, JC, Hein, JE, Tantillo, DJ, Fox, JM & Shaw, JT 2017, 'Synthesis of Benzodihydrofurans by Asymmetric C−H Insertion Reactions of Donor/Donor Rhodium Carbenes', Chemistry - A European Journal, vol. 23, no. 49, pp. 11843-11855. https://doi.org/10.1002/chem.201701630
Lamb, Kellan N. ; Squitieri, Richard A. ; Chintala, Srinivasa R. ; Kwong, Ada J. ; Balmond, Edward I. ; Soldi, Cristian ; Dmitrenko, Olga ; Castiñeira Reis, Marta ; Chung, Ryan ; Addison, J. Bennett ; Fettinger, James C. ; Hein, Jason E. ; Tantillo, Dean J. ; Fox, Joseph M. ; Shaw, Jared T. / Synthesis of Benzodihydrofurans by Asymmetric C−H Insertion Reactions of Donor/Donor Rhodium Carbenes. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 49. pp. 11843-11855.
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