Research ArticleBIOCHEMISTRY

Radical chain repair: The hydroalkylation of polysubstituted unactivated alkenes

See allHide authors and affiliations

Science Advances  20 Jul 2018:
Vol. 4, no. 7, eaat6031
DOI: 10.1126/sciadv.aat6031
  • Scheme 1 Strategies for the radical hydroalkylation of unactivated alkenes.

    EWG, electron-withdrawing group. New bonds are indicated in bold blue.

  • Scheme 2 Radical hydroalkylation of terminal and nonterminal alkenes.
  • Scheme 3 Bis-hydroalkylation of (−)-β-pinene with ethyl chloroiodoacetate and hydroalkylation of cholesteryl benzoate with N-Cbz-O-iodoacetyl serine.
  • Scheme 4 Mechanistic studies.

    (C and D) Hydroalkylation of n-3-hexene and bicyclohexylidene showing a non-regioselective repair process. (E) Mechanism of the hydroalkylation process highlighting the productive chain process (in black), the retarding reactions (in red), and the repair process (in green).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/4/7/eaat6031/DC1

    General information

    General procedures

    Characterized products

    Study of the repair process

    Kinetic studies

    1H- and 13C-NMR spectra

    Fig. S1. Analysis by GC [Tinitial = 50°C (1 min) to Tfinal = 180°C (20 min), at 8°C/min] of the crude reaction product shows the presence, beside the major product 37, of the regioisomer 38 (1%).

    Fig. S2. GC analysis of the product (mixture of 37 and 38).

    Fig. S3. GC analysis of the crude reaction product after ozonolysis.

    Fig. S4. GC analysis of the crude reaction product after treatment with ozone and addition of a pure sample of 20 (mixture of diastereomers).

    Fig. S5. GC of the crude reaction mixture before evaporation of the solvents.

    Fig. S6. GC of the crude reaction mixture before evaporation of the solvent showing the presence of the deiodinated CH3CO2Bn (9.69 min), bicyclohexylidene (11.90 min), and 1-cyclohexylcyclohexene (11.84 min).

    Fig. S7. GC of the crude reaction mixture before and after treatment with Et3B/TBC.

    Fig. S8. Plot of [S2]/([S3]+[S4]) against the concentration of TBC.

    Fig. S9. Determination of the relative configuration of S3 based on 3J 1H-NMR coupling constants.

    Scheme S1. Radical clock experiment with S1.

    References (3642)

  • Supplementary Materials

    This PDF file includes:

    • General information
    • General procedures
    • Characterized products
    • Study of the repair process
    • Kinetic studies
    • 1H- and 13C-NMR spectra
    • Fig. S1. Analysis by GC Tinitial = 50°C (1 min) to Tfinal = 180°C (20 min), at 8°C/min of the crude reaction product shows the presence, beside the major product 37, of the regioisomer 38 (1%).
    • Fig. S2. GC analysis of the product (mixture of 37 and 38).
    • Fig. S3. GC analysis of the crude reaction product after ozonolysis.
    • Fig. S4. GC analysis of the crude reaction product after treatment with ozone and addition of a pure sample of 20 (mixture of diastereomers).
    • Fig. S5. GC of the crude reaction mixture before evaporation of the solvents.
    • Fig. S6. GC of the crude reaction mixture before evaporation of the solvent showing the presence of the deiodinated CH3CO2Bn (9.69 min), bicyclohexylidene (11.90 min), and 1-cyclohexylcyclohexene (11.84 min).
    • Fig. S7. GC of the crude reaction mixture before and after treatment with Et3B/TBC.
    • Fig. S8. Plot of S2/(S3+S4) against the concentration of TBC.
    • Fig. S9. Determination of the relative configuration of S3 based on 3J 1H-NMR coupling constants.
    • Scheme S1. Radical clock experiment with S1.
    • References (3642)

    Download PDF

    Files in this Data Supplement:

Navigate This Article