- Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes with Simple Ketones
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We developed a highly regioselective addition of 1,3-dienes with simple ketones by nickel-hydride catalyst bearing DTBM-SegPhos ligand. A wide range of aromatic and aliphatic ketones directly coupled with 1,3-dienes, providing synthetically useful γ,δ-unsaturated ketones in high yield and regioselectivity. The asymmetric version of the reaction was also realized in high enantioselectivity by using novel chiral ligand DTBM-HO-BIPHEP. The utility of this hydroalkylation was demonstrated by facile product modification and enantioselective synthesis of (R)-flobufen.
- Cheng, Lei,Li, Ming-Ming,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 11627 - 11630
(2018/09/21)
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- Regio- and Enantioselective Copper-Catalyzed 1,4-Conjugate Addition of Trimethylaluminium to Linear α,β,γ,δ-Unsaturated Alkyl Ketones
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A regio- and enantioselective copper-catalyzed 1,4-conjugate addition of trimethylaluminium to linear δ-aryl-substituted α,β,γ,δ-unsaturated alkyl ketones was developed. A series of γ,δ-unsaturated alkyl ketones were obtained in good yields with high regio- and enantioselectivity (up to 88% ee and 96:4 dr). Expansion of the reaction scope to substrates containing aromatic heterocycles also afforded good yields and enantioselectivities (up to 91% ee) with very high regioselectivities, exclusively providing the single 1,4-products. (Figure presented.).
- Wu, Xiaoting,Xie, Fang,Ling, Zheng,Tang, Liang,Zhang, Wanbin
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p. 2510 - 2518
(2016/08/16)
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- Chiral [2.2.2] dienes as ligands for Rh(I) in conjugate additions of boronic acids to a wide range of acceptors
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We document a series of investigations that led to new substituted [2.2.2]-diene ligands which display high selectivity in Rh(I)-catalyzed conjugate addition reactions to substrates not previously examined with diene ligands. Moreover, we disclose an unexpected, interesting effect that results from the introduction of a third C=C onto the ligand scaffold (cf. 1).
- Defieber, Christian,Paquin, Jean-Francois,Serna, Sonia,Carreira, Erick M.
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p. 3873 - 3876
(2007/10/03)
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- Stereo- and Regiochemistry in Palladium-Catalyzed Nucleophilic Substitution of Optically Active (E)- and (Z)-Allyl Acetates
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Optically acive (E)- and (Z)-allyl acetates, 3-acetoxy-1-phenyl-1-butene (1) and its regioisomer, 1-acetoxy-1-phenyl-3-butene (2), were allowed to react with sodium dimethyl malonate, sodium acetylacetonate, and sodium methyl acetoacetate in the presence of a palladium catalyst.The reaction of (E)-acetates proceeded with retention of configuration and that of (Z)-acetates proceeded with inversion accompanied by geometrical isomerization from Z to E.The stereochemistry observed in the reaction with phenylzinc bromide was opposite to that with the soft nucleophiles.
- Hayashi, Tamio,Yamamoto, Akihiro,Hagihara, Toshiya
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p. 723 - 727
(2007/10/02)
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