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. 2018 May 23;9(23):5284-5288.
doi: 10.1039/c8sc01538d. eCollection 2018 Jun 21.

Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes

Yangbin Liu  1 , Daniele Fiorito  1 , Clément Mazet  1
Affiliations

Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes

Yangbin Liu et al. Chem Sci. .

Abstract

A highly enantioselective Cu-catalyzed borylation of 2-substituted 1,3-dienes is reported. The use of a chiral phosphanamine ligand is essential in achieving high chemo-, regio-, diastereo- and enantioselectivity. It provides access to a variety of homoallylic boronates in consistently high yield and enantiomeric excess with 2-aryl and 2-heteroaryl 1,3-dienes as well as sterically demanding 2-alkyl 1,3-dienes. Preliminary investigations based on a non-linear effect study point to a mechanism involving more than one metal center.

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Figures

Fig. 1
Fig. 1. (A) Linear vs. 2-substituted conjugated 1,3-dienes. (B) Selectivity challenges in hydroboration and borylation of 2-substituted 1,3-dienes. (C) Previous hydroborations/borylations of 2-substituted 1,3-dienes. (D) Arylboration of isoprene along with putative primary and tertiary Cu σ-allyl intermediates.
Fig. 2
Fig. 2. Sequential borylation/oxidation of 2-(hetero)aryl substituted 1,3-dienes. Reaction conditions: 1a (0.36 mmol), B2(pin)2 (0.30 mmol). Chemoselectivity assessed by 1H NMR after borylation. Yields of isolated alcohols 2′. Enantioselectivity determined after oxidation by HPLC, GC or SFC using a chiral stationary phase. aThe minor isomer is 4′n. bIsolated as a 5 : 1 mixture.
Fig. 3
Fig. 3. Sequential borylation/oxidation of 2-alkyl substituted 1,3-dienes. Reaction conditions: 1u-x (0.18–0.36 mmol), B2(pin)2 (0.15–0.30 mmol). Chemoselectivity assessed by 1H NMR after borylation. Isolated yields for alcohols 2′v-x. Enantioselectivity determined after oxidation by HPLC, GC, SFC using a chiral stationary phase. aConversion of non-separable isomers determined by 1H NMR (2′u + 3′u). bAt 0 °C for 24 h.
Fig. 4
Fig. 4. Non-linear effect study. Reaction conditions: 1a (0.12 mmol), B2(pin)2 (0.10 mmol). Chemoselectivity > 20 : 1 in all cases as assessed by 1H NMR. Enantioselectivity determined after oxidation by HPLC using a chiral stationary phase. Average of two experiments.
Fig. 5
Fig. 5. Catalyst-controlled diastereoselective borylation of (S)-1y. Reaction conditions: (S)-1y (0.24 mmol), B2(pin)2 (0.20 mmol). Chemoselectivity > 20 : 1 in all cases as assessed by 1H after borylation. Diastereoselectivity assessed by 1H and 13C{1H} NMR after borylation and oxidation. Isolated yields after oxidation.
Fig. 6
Fig. 6. Borylation/oxidation sequence of bis-diene 1z (0.36 mmol scale). a1,2-/4,3-selectivity = 10 : 1. bInseparable mixture.
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