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A general, modular method for the catalytic asymmetric synthesis of alkylboronate esters

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Science  09 Dec 2016:
Vol. 354, Issue 6317, pp. 1265-1269
DOI: 10.1126/science.aai8611
  • Fig. 1 Alkylboronate esters.

    (A to D) Background. (E to G) This study. R, alkyl group (superscripts indicate different alkyl groups); Me, methyl; pin, pinacolato; THF, tetrahydrofuran; DMA, dimethylacetamide; equiv, equivalent; ee, enantiomeric excess.

  • Fig. 2 Nickel-catalyzed asymmetric synthesis of alkylboronate esters.

    (A and B) Variation in the coupling partners. The ee was determined by chiral high-performance liquid chromatography after oxidation to the alcohol. The yield was determined by isolation after chromatographic purification. (C) Functional-group compatibility. (D) Comparison of the enantioselectivity-determining step when using a chiral auxiliary versus a chiral catalyst. All data represent the average of two experiments. *α-iodoboronate was used. †Reaction temperature, 10°C. ‡Catalyst loading, 12% NiBr2•diglyme and 16% L*. TBS, tert-butyldimethylsilyl; Ac, acetyl; Ph, phenyl; Boc, t-butoxycarbonyl.

  • Fig. 3 Catalyst-controlled stereoselectivity in the asymmetric synthesis of alkylboronate esters.

    (A) Complex coupling partners. (B) Iterative homologation. d.r., diastereomeric ratio.

  • Fig. 4 Enantioenriched alkylboronate esters as versatile intermediates.

    The alkylboronate compounds are converted to diverse families of organic molecules through C–C, C–N, C–O, and C–halogen bond formation. NBS, N-bromosuccinimide; LDA, lithium diisopropylamide; TBAF, tetrabutylammonium fluoride; ArLi, [3,5-bis(trifluoromethyl)phenyl]lithium; NIS, N-iodosuccinimide.

Supplementary Materials

  • A general, modular method for the catalytic asymmetric synthesis of alkylboronate esters

    Jens Schmidt, Junwon Choi, Albert Tianxiang Liu, Martin Slusarczyk, Gregory C. Fu

    Materials/Methods, Supplementary Text, Tables, Figures, and/or References

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    • Materials and Methods
    • Supplementary Text
    • Tables S1 to S7
    • Spectral Data
    • References

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