- The first allylation of imines with allyltrichlorosilanes using neutral coordinate-organocatalysts
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Imines derived from aldehydes and 2-aminophenols reacted with allyltrichlorosilanes in the presence of DMF, HMPA, or pyridine N-oxide as a neutral coordinate-organocatalyst to afford the corresponding homoallylic amines in high yields with high stereosele
- Sugiura, Masaharu,Robvieux, Fabrice,Kobayashi, Shu
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- Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines
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N-(Aryloxy)imines, readily accessible by condensation/tautomerization of (pseudo)benzylic primary amines and 2,6-di-tert-butyl-1,4-benzoquinone, undergo efficient allylation to afford a wide range of homoallylic primary amines following hydrolytic workup. Deprotonation of N-(aryloxy)imines generates a delocalized 2-azaallyl anion-type nucleophile that engages in dearomative C-C bond-forming reactions with allylpalladium(II) electrophiles generated from allylic tert-butyl carbonates. This reactivity umpolung enables the formal α-allylation of (pseudo)benzylic primary amines. Mechanistic studies reveal that the apparent regioselectivity of the desired bond-forming event is a convergent process that is initiated by unselective allylation of N-(aryloxy)imines to give several regioisomeric species, which subsequently rearrange via stepwise [1,3]- or concerted [3,3]-sigmatropic shifts, ultimately converging to provide the desired regioisomer of the amine products.
- Mori-Quiroz, Luis M.,Londhe, Shrikant S.,Clift, Michael D.
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p. 14827 - 14846
(2020/12/02)
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- Characterization and utility of N-unsubstituted imines synthesized from alkyl azides by ruthenium catalysis
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Shine a light: A fluorescent light-induced synthetic method for the title compounds has been developed and the chemoselective nature of the reaction is highlighted by the observation of the cis/trans isomers of various N-unsubstituted imines. The synthetic utility of this method is demonstrated by the one-pot imine formation/asymmetric allylation sequence of benzyl azide catalyzed by 1. (Ipc=isopinocampheyl). Copyright
- Lee, Jin Hee,Gupta, Sreya,Jeong, Wook,Rhee, Young Ho,Park, Jaiwook
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supporting information
p. 10851 - 10855
(2013/01/15)
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- α-aminoallylation of aldehydes with ammonia: Stereoselective synthesis of homoallylic primary amines
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Three-component reactions of aldehydes, ammonia, and allylboronates were found to provide homoallylic primary amines in high yields with high chemo- and stereoselectivities. A two-step, one-pot, stereoselective synthesis of an uncommon α-amino acid, alloisoleucine, was achieved utilizing this reaction. Copyright
- Sugiura, Masaharu,Hirano, Keiichi,Kobayashi, Shu
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p. 7182 - 7183
(2007/10/03)
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- Highly stereoselective synthesis of homoallylic amines based on addition of allyltrichlorosilanes to benzoylhydrazones
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Allyltrichlorosilanes reacted with benzoylhydrazones in DMF without the use of any catalyst to afford the corresponding homoallylic benzoylhydrazines in good to high yields. The reactions proceeded at 0°C to room temperature under mild conditions. In addi
- Hirabayashi,Ogawa,Sugiura,Kobayashi
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p. 9493 - 9499
(2007/10/03)
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- Diastereoselective Addition of Crotylboronates to Oximes
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The addition of E- and Z-crotylboronates 8,9 to aldoximes has been realized in good yields by running the reaction under 4-9 kbar pressure.The direction of the attendant diastereoselectivity was surprising: E-8 led preferentially to the anti-, Z-9 to the syn-N-(β-methylalkyl)hydroxylamines 10, 11.
- Hoffmann, Reinhard W.,Endesfelder, Andreas
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p. 215 - 220
(2007/10/02)
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