Nickel Catalyzed Intermolecular Carbonyl Addition of Aryl Halide

Abstract

In this study, we develop a nickel‐catalyzed carbonyl arylation reaction employing aldehydes with aryl and allyl halides. Various aryl, α,β‐unsaturated aldehyde and aliphatic aldehydes can be converted into their corresponding secondary alcohols in moderate‐to‐high yields. In addition, we extended this approach to develop an asymmetric reductive coupling reaction that combines nickel salts with chiral bisoxazoline ligands to give secondary alcohols with moderate enantioselectivity.

Nickel-Catalyzed Reductive Allylation of Aldehydes with Allyl Acetates

“…Conversely, we have previously developed a reductive carbonyl addition reaction of aldehydes with aryl halides catalyzed by a nickel complex (Scheme 1c). 13 In the original report, the aryl halide transforms into a transient nucleophile under Ni catalysis. Driven by the authors' interest in carbonyl addition chemistry, the research focused on the synthesis of homoallyl alcohols by the reaction of carbonyl with allyl acetate via Ni catalysis.…”

“…All dry solvents were obtained from Kanto Kagaku Co., Ltd. and Wako Pure Chemical Industries, Ltd. Other chemicals used were of reagent grade and were obtained from Tokyo Kasei Kogyo Co., Ltd., Wako Pure Chemical Industries, Ltd., Nacalai Tesque, and Sigma Aldrich Co., Ltd. 1 H NMR, 13 C NMR, and 19 F NMR spectra were obtained on a JEOL AL 400 instrument at room temperature of samples in CDCl 3 as a solvent (400 MHz for 1 H NMR, 100 MHz for 13 C NMR). Chemical shifts () are expressed in parts per million and are internally referenced [ = 0.00 (TMS) for 1 H NMR and  = 77.0 (CDCl 3 ) for 13 C NMR]. TLC was carried out on precoated plates of silica gel (Merck, silica gel F-254, 0.5 mm).…”

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.26-7.08 (m, 4 H), 5.86-5.76 (m, 1 H), 5.19-5.13 (m, 2 H), 4.71-4.68 (m, 1 H), 2.52-2.46 (m, 2 H), 2.36 (s, 3 H), 2.03 (br s, 1 H). 13 C NMR (100 MHz, CDCl 3 ):  = 143.9, 138.2, 134.7, 128.4, 128.4, 126.6, 123.0, 118.5, 73.4, 44.0, 21.6.…”

“…NMR (400 MHz, CDCl 3 ):  = 7.48 (d, J = 7.8 Hz, 1 H), 7.25-7.12 (m, 3 H), 5.91-5.81 (m, 1 H), 5.21-5.14 (m, 2 H), 4.98 (m, 1 H), 2.54-2.39 (m, 2 H) 2.34 (s, 3 H), 1.96 (s, 1 H) 13. C NMR (100 MHz, CDCl 3 ):  = 141.9, 134.7, 134.3, 130.3, 127.2, 126.2, 125.1, 118.3, 69.6, 42.6, 19.0.1-Phenylbut-3-en-1ol (3da) 24Yield: 29.3 mg (0.20 mmol, 66%); colorless oil.…”

“…TLC (silica gel): R f = 0.33 (n-hexane/EtOAc, 10:1) 1. H NMR (400 MHz, CDCl 3 ):  = 7.38-7.27 (m, 5 H), 5.86-5.78 (m, 1 H), 5.20-5.14 (m, 2 H), 4.75 (ddd, J = 8.0, 4.6, 2.9 Hz, 1 H), 2.47-2.57 (m, 2 H) 13. C NMR (100 MHz, CDCl 3 ):  = 143.8, 134.4, 128.4, 127.6, 125.8, 118.5, 73.3, 43.9.1-(4-Methoxyphenyl)but-3-en-1-ol (3ea) 24Yield: 45.4 mg (0.26 mmol, 85%); colorless oil.…”