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. 2019 Oct 4;9(54):31654-31658.
doi: 10.1039/c9ra05532k. eCollection 2019 Oct 1.

Enantioselective bromination of axially chiral cyanoarenes in the presence of bifunctional organocatalysts

Yuuki Wada  1 , Akira Matsumoto  1 , Keisuke Asano  1 , Seijiro Matsubara  1
Affiliations

Enantioselective bromination of axially chiral cyanoarenes in the presence of bifunctional organocatalysts

Yuuki Wada et al. RSC Adv. .

Abstract

Enantioselective bromination of axially chiral cyanoarenes bearing high intrinsic rotational barriers via dynamic kinetic resolution using bifunctional organocatalysts is reported. Sequential addition of a brominating reagent in several portions at an optimized temperature was effective in accomplishing high enantioselectivities.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Enantioselective bromination of axially chiral cyanoarenes using bifunctional organocatalysts.
Fig. 1
Fig. 1. Brominating reagents.
Fig. 2
Fig. 2. Investigations of temperatures and procedures. Blue bar: reactions were run with 4a added in 1 portion. Red bar: reactions were run with 4a added in 5 portions. Green values represent yields of 2a isolated after silica gel column chromatography. At 0, −10, −20, and −30 °C, reactions were run for 24 h; at −40 °C, reactions were run for 72 h.
Fig. 3
Fig. 3. Relationships between ee and yield. Red line: reactions were run at −30 °C for 24 h with 4a added in 5 portions. Blue line: reactions were run at −40 °C for 72 h with 4a added in 5 portions. Red and blue values represent amounts of 4a used for each reaction.
Fig. 4
Fig. 4. Rotational barriers of substrate, intermediate, and product calculated at the M06-2X/6-311++G(2d,3p)//B3LYP/6-31+G(d,p) level of theory.
Scheme 2
Scheme 2. Reactions of substrates with substituted phenols. aReaction was run for 72 h.
Scheme 3
Scheme 3. Reactions with a substoichiometric amount of 4a.
See this image and copyright information in PMC

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