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. 2017 Dec 18;56(51):16352-16356.
doi: 10.1002/anie.201709334. Epub 2017 Nov 24.

Enantioselective Rhodium-Catalyzed Coupling of Arylboronic Acids, 1,3-Enynes, and Imines by Alkenyl-to-Allyl 1,4-Rhodium(I) Migration

Michael Callingham  1   2 , Benjamin M Partridge  1   3 , William Lewis  1 , Hon Wai Lam  1   2
Affiliations

Enantioselective Rhodium-Catalyzed Coupling of Arylboronic Acids, 1,3-Enynes, and Imines by Alkenyl-to-Allyl 1,4-Rhodium(I) Migration

Michael Callingham et al. Angew Chem Int Ed Engl. .

Abstract

A chiral rhodium complex catalyzes the highly enantioselective coupling of arylboronic acids, 1,3-enynes, and imines to give homoallylic sulfamates. The key step is the generation of allylrhodium(I) species by alkenyl-to-allyl 1,4-rhodium(I) migration.

Keywords: allylation; asymmetric catalysis; imines; isomerization; rhodium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Catalytic enantioselective three‐component nucleophilic allylations.
Scheme 2
Scheme 2
Variation of the imine. Reactions employed 0.30 mmol of the imine. Diastereomeric ratios were determined by 1H NMR analysis of the crude reactions. Yields are of isolated diastereomerically pure products. Enantiomeric excesses were determined by HPLC analysis on a chiral stationary phase. [a] Using 0.20 mmol of imine 1 e.
Scheme 3
Scheme 3
Variation of the 1,3‐enyne. See the footnote of Scheme 2 for general considerations. [a] Using 1.5 equiv of 1,3‐enyne 2 b. [b] Using 3.0 equiv each of PhB(OH)2 and tAmOH. [c] Using 1.5 equiv of 1,3‐enyne 2 g and 2.0 equiv each of PhB(OH)2, KF, and tAmOH. [d] An 8.2:1 inseparable mixture of 3 o and the imine phenylation product was obtained (the yield of 3 o has been adjusted accordingly).
Scheme 4
Scheme 4
Variation of the arylboronic acid. See the footnote of Scheme 2 for general considerations. [a] Isolated in approximately 91 % purity (the yield has been adjusted accordingly). [b] Using 1.5 equiv of 1,3‐enyne 2 a.
Scheme 5
Scheme 5
Proposed catalytic cycle.
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