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. 2023 Jul 21;25(28):5297-5301.
doi: 10.1021/acs.orglett.3c01849. Epub 2023 Jul 12.

Stereospecific Cu(I)-Catalyzed C-O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

San L Pham  1 , Taehee Kim  1 , Frank E McDonald  1
Affiliations

Stereospecific Cu(I)-Catalyzed C-O Cross-Coupling Synthesis of Acyclic 1,2-Di- and Trisubstituted Vinylic Ethers from Alcohols and Vinylic Halides

San L Pham et al. Org Lett. .

Abstract

CuI and trans-N,N'-dimethylcyclohexyldiamine catalyze the single-step C-O bond cross-coupling between 1,2-di- and trisubstituted vinylic halides with functionalized alcohols, producing acyclic vinylic ethers. This stereospecific transformation selectively gives each of the (E)- and (Z)-vinylic ether products from the corresponding vinyl halide precursors. This method is compatible with carbohydrate-derived primary and secondary alcohols and several other functional groups. The conditions are mild enough to reliably generate vinylic allylic ethers without promoting Claisen rearrangements.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Stereoselective syntheses of 1,2-disubstituted vinylic ethers from alcohols.
Figure 2
Figure 2
Scope of (E)- and (Z)-vinylic ethers synthesized from stereoselective cross-couplings with (a) primary alcohols and with (b) secondary alcohols, with isolated yields. (Z)/(E) ratios determined by 1H NMR analysis prior to chromatographic purification.
Figure 3
Figure 3
Scope of cross-coupling products with other vinylic halides.
See this image and copyright information in PMC

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