- One-Pot Synthesis of Primary and Secondary Aliphatic Amines via Mild and Selective sp3 C?H Imination
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The direct replacement of sp3 C?H bonds with simple amine units (?NH2) remains synthetically challenging, although primary aliphatic amines are ubiquitous in medicinal chemistry and natural product synthesis. We report a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot, based on intermolecular sp3 C?H imination. The first C?H imination of diverse alkanes, this method shows useful site-selectivity within substrates bearing multiple sp3 C?H bonds. Furthermore, this reaction tolerates polar functional groups relevant for complex molecule synthesis, highlighted in the synthesis of amine pharmaceuticals and amination of natural products. We characterize a unique C?H imination mechanism based on radical rebound to an iminyl radical, supported by kinetic isotope effects, stereoablation, resubmission, and computational modeling. This work constitutes a selective method for complex amine synthesis and a new mechanistic platform for C?H amination.
- Comito, Robert J.,Ghosh, Subrata K.,Hu, Mengnan
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supporting information
p. 17601 - 17608
(2021/11/03)
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- Synthesis of sultams by intramolecular Heck reaction
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A novel access to α-methylene-γ-sultams via the intramolecular Heck reaction of α-bromovinylsulfonamides derived from allylic amines is reported. These heterocycles are potent Michael acceptors towards sulfur nucleophiles.
- Merten, Sandra,Froehlich, Roland,Kataeva, Olga,Metz, Peter
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p. 754 - 758
(2007/10/03)
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- Asymmetric synthesis of primary amines from alkenes and chiral chloronitroso sugar derivatives
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A variety of alkenes 5 - 15, 38, 39 react with chloronitroso sugar derivatives 1 - 3 regioselectively at ambient temperature to give chiral hydroxylamines in 60-80% yield. In addition to these products of a formal ene reaction joined by a subsequent hydro
- Braun,Felber,Kresse,Ritter,Schmidtchen,Schneider
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p. 3313 - 3328
(2007/10/20)
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- An Efficient Route to Both Enantiomers of N-(p-Tolylsulfonyl)-benzenesulfonimidamide and Their Use for Asymmetric Allylic Amination of Olefins
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The chiral compounds (R)- and (S)-N-(p-tolylsulfonyl)benzenesulfonimidamide have been prepared effiently from N-(p-tolylsulfonyl)benzenesulfonimidoyl chloride and both enenatiomers were transformed into chiral selenium diimide reagents, (S)- and (R)-N,N'-
- Tsushima, Susumu,Yamada, Yasuhiro,Onami, Tetsuo,Oshima, Koichiro,Chaney, Michael O.,et all.
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p. 1167 - 1178
(2007/10/02)
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- PALLADIUM(0) CATALYZED AZIDATION AND AMINATION OF ALLYL ACETATES. SELECTIVE SYNTHESIS OF ALLYL AZIDES AND PRIMARY ALLYLAMINES
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Palladium catalyzed reaction of allyl acetates with azide ion gives allyl azides, which are readily converted into the corresponding primary allylamines upon treatment with PPh3/NaOH.
- Murahashi, Shun-Ichi,Tanigawa, Yoshio,Imada, Yasushi,Taniguchi, Yuki
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p. 227 - 230
(2007/10/02)
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