Synthesis of Enantiopure 1‐Aryl‐1‐butylamines and 1‐Aryl‐3‐butenylamines by Diastereoselective Addition of Allylzinc Bromide to Imines Derived from (<i>R</i>)‐Phenylglycine Amide

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.

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“…13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ 144.8, 135.0, 131.5, 128.2, 120.7, 118.1, 54.8, 44.2. Spectral data are in accordance with published values …”

Section: Methodssupporting

confidence: 86%

Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines

2020

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“…The absolute configuration of bis‐homoallylamines 5 was determined by hydrogenation of 5e to afford the known compound 1‐(4‐methoxyphenyl)‐butan‐1‐amine 9 (Scheme ) by debenzylation of the p ‐xylene moiety. The specific optical rotation of 9 [α] D 25 =11.5 ( c 3.0, CHCl 3 ) matched very well with reported data, lit . [α] D 25 =12.57 ( c 7.39, CHCl 3 ).…”

Section: Resultssupporting

confidence: 86%

(−)‐β‐Pinene‐based π‐Allylpalladium Complex‐Catalyzed Asymmetric Allylation of Bis‐Imines

Fernandes

Nallasivam

2020

ChemistrySelect

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(−)‐β‐Pinene‐based η3‐π‐allylpalladium complex has shown the efficacy in the catalytic asymmetric allylation of para‐ and meta‐xylene spaced bis‐arylimines. The complex has catalyzed asymmetric allylation of various bis‐imines in the presence of allyltributylstannane and two equivalents of water to furnish chiral bis‐homoallylamines in moderate to good yields (up to 70%) and enantioselectivities up to 98.6 : 1.4 er.

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“…We employed the known chiral amines 7 and 8 as the starting materials for the desired amines 11a-12c, Scheme 1. [26,27] The protection of the amino function in 7 and 8 using t-butoxycarbonyl (t-BOC) enabled Suzuki coupling with three different aryl boronic acids. After Suzuki coupling, the removal of the t-BOC with CF 3 CO 2 H produced chiral amines 11a-12c.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of novel chiral [(NHC)Au(I)Cl] complexes: Featuring ortho-biphenyl substituents

Holmes

Manganaro

Barnes

et al. 2015

Journal of Organometallic Chemistry

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A series of new chiral [(NHC)Au(I)Cl] are synthesized. The chiral NHC ligands feature pairs of ortho-biphenyl groups. The distal phenyl groups of the biphenyl substituents are varied from simple phenyl, 3,5-dimethylphenyl, to 3,5-di-t-butylphenyl. X-Ray structure analysis were performed for two such [(NHC)Au(I)Cl] complexes. High percent buried volumes were calculated for two novel chiral [(NHC)Au(I)Cl]complexes whose structure were solved by an X-ray analysis. The rotational motion in the biphenyl group is slow on the NMR time scale. Rotational barriers were determined using WINDNMR for two of the chiral gold complexes.

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Synthesis of Enantiopure 1‐Aryl‐1‐butylamines and 1‐Aryl‐3‐butenylamines by Diastereoselective Addition of Allylzinc Bromide to Imines Derived from (R)‐Phenylglycine Amide

Cited by 23 publications

References 50 publications

Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines

Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines

(−)‐β‐Pinene‐based π‐Allylpalladium Complex‐Catalyzed Asymmetric Allylation of Bis‐Imines

Synthesis and characterization of novel chiral [(NHC)Au(I)Cl] complexes: Featuring ortho-biphenyl substituents

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