Anti‐Markovnikov Hydroamination of Racemic Allylic Alcohols to Access Chiral γ‐Amino Alcohols

Xu, Ruirui; Wang, Kun; Liu, Haoying; Tang, Weijun; Sun, Huaming; Duan, Xue; Xiao, Jianliang; Wang, Chao

doi:10.1002/anie.202009754

Cited by 63 publications

(34 citation statements)

References 129 publications

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“…Recently, Wang and co‐workers employed chiral ruthenium catalysts – similar to Noyori's catalysts – for the asymmetric hydroamination of allylic alcohols with piperazines [13] . Complementary to these original publications, the Buchwald group reported a copper‐phosphine catalyst, in conjunction with silanes, to obtain asymmetric γ‐amino alcohols using hydroxyl amines as nucleophiles [14] .…”

Section: Methodsmentioning

confidence: 99%

Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP‐Pincer Complexes

et al. 2021

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Section: Methodsmentioning

confidence: 99%

Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP‐Pincer Complexes

et al. 2021

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“…3-(benzyl(methyl)amino)-1-phenylpropan-1-ol (3it): 17 In an oven-dried 15 mL reaction tube, allyl alcohol (1i, 1.0 mmol, 134 mg), Mn1 (0.005 mmol, 2.4 mg), K2CO3 (0.18 mmol, 24.2 mg) was added followed by the addition of toluene (0.25 mL), i PrOH (0.75 mL), and amine (2t, 0.25 mmol, 20 μL) under Ar. The tube was sealed and transferred to a preheated oil bath at 100 o C. After 12 h the reaction mixture was cooled, passed through a short plug of Na2SO4 and eluted wit DCM (2 × 3 mL).…”

Section: S21mentioning

confidence: 99%

“…On the other hand, the modern era of organometallic synthesis demands the development of catalysts based on Earth's abundant transition metals due to easy accessibility, low cost, and less toxicity. 17 Moreover, the reported protocols used phosphine-based ligands, which are comparatively expensive and prone to undergo degradation under aerial condition such that the beneficial effect of the cheap metal catalysts is often forfeited. Hence, a combination of 3d-transition metal, and a readily available bench-stable ligand, is highly appreciable at present for the anti-Markovnikov hydroamination of allylic alcohols for the synthesis of valuable γ-amino alcohols.…”

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confidence: 99%

Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis

2021

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Controlling the selectivity in hydroamination reaction is an extremely challenging yet highly desirable task for the selective diversification of amines. In this manuscript, a selective formal anti-Markovnikov hydroamination of allyl alcohols is presented. It enables the versatile synthesis of valuable γ-amino alcohol building blocks. A phosphine-free Earth's abundant manganese(I) complex catalyzed the reaction under hydrogen borrowing conditions. A vast range of aliphatic, aromatic amines, drug molecules, and natural product derivatives underwent successful hydroamination with primary and secondary allylic alcohols with excellent functional group tolerance (57 examples). The catalysis could be performed on a gram scale and have been applied for the synthesis of drug molecules. The mechanistic studies revealed the metal-ligand bifunctionality as well as hemilability of the ligand backbone as the key design principle for the success of this catalysis. needed to be highly chemoselective for catalyzing anti-Markovnikov hydroamination reaction, avoiding competing reduction of C = X (X = C, N) bonds, 21 allylic substitution, 5s, 22 and allylic isomerization. 23 Scheme 1. a) Drug Molecules Prepared from γ-Amino Alcohols. b) Metal Catalyzed Homogeneous Anti-Markovnikov Hydroamination of Allyl Alcohol.sidearm to be the salient factors operating to the success of this waste-free hydrogen transfer catalysis. ASSOCIATED CONTENT Supporting InformationThe Supporting Information is available free of charge via the Internet at http://pubs.acs.org. Experimental procedures, analytical data, kinetic data, NMR spectra of compounds and complexes.

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“…Enantioselective variants of these transformations, on the other hand, have remained underdeveloped 22 , 23 . Highly enantioselective alkylation of amines and ketones has only been achieved in recent years by our group 24 – 28 , the Beller group 29 , the Donohoe group 30 , 31 , and others 32 – 37 to access chiral amines, ketones, alcohols, etc. The application of borrowing hydrogen strategy to an enantioconvergent heteroarylation, to our knowledge, has never been reported in the literature 38 .…”

Section: Introductionmentioning

confidence: 99%

Redox-enabled direct stereoconvergent heteroarylation of simple alcohols

et al. 2021

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The direct transformation of racemic feedstock materials to valuable enantiopure compounds is of significant importance for sustainable chemical synthesis. Toward this goal, the radical mechanism has proven uniquely effective in stereoconvergent carbon-carbon bond forming reactions. Here we report a mechanistically distinct redox-enabled strategy for an efficient enantioconvergent coupling of pyrroles with simple racemic secondary alcohols. In such processes, chirality is removed from the substrate via dehydrogenation and reinstalled in the catalytic reduction of a key stabilized cationic intermediate. This strategy provides significant advantage of utilizing simple pyrroles to react with feedstock alcohols without the need for leaving group incorporation. This overall redox-neutral transformation is also highly economical with no additional reagent nor waste generation other than water. In our studies, oxime-derived iridacycle complexes are introduced, which cooperate with a chiral phosphoric acid to enable heteroarylation of alcohols, accessing a wide range of valuable substituted pyrroles in high yield and enantioselectivity.

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Anti‐Markovnikov Hydroamination of Racemic Allylic Alcohols to Access Chiral γ‐Amino Alcohols

Cited by 63 publications

References 129 publications

Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP‐Pincer Complexes

Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP‐Pincer Complexes

Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis

Redox-enabled direct stereoconvergent heteroarylation of simple alcohols

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