N,N′-Dioxide–nickel(II) complex catalyzed asymmetric Michael addition of cyclic 1,3-dicarbonyl compounds to β,γ-unsaturated α-ketoesters

Dong, Zhenhua; Feng, Juhua; Cao, Weidi; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming

doi:10.1016/j.tetlet.2011.04.089

Cited by 52 publications

(26 citation statements)

References 42 publications

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“…Later, several groups reported the successful use of various organocatalysts in these reactions. In 2011, Lin and Feng applied an N,N′‐ dioxide chiral nickel(II) catalyst to induce the enantioselective domino Michael/cyclization reaction of cyclic 1,3‐dicarbonyl compounds to β,γ‐unsaturated α‐keto esters 82. The catalyst was in situ generated from Ni(acac) 2 and chiral N,N′‐ dioxide 48 , both employed at 5 mol% of catalyst loading in 1,2‐dichloroethane in the presence of molecular sieves at 0 °C.…”

Section: Domino and Tandem Processes Initiated By A Michael Reactionmentioning

confidence: 99%

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

Pellissier

2015

Adv Synth Catal

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International audienceDuring the last ten years, an important number of novel highly efficient asymmetric conjugate additions of various nucleophiles to numerous acceptor-activated olefins have been developed on the basis of asymmetric nickel(II) catalysis by the very fact of the lower costs of nickel catalysts in comparison with other transition metals. These processes can be considered as one of the most powerful and reliable tools for the stereocontrolled formation of carbon-carbon bonds. Importantly, a range of fascinating nickel-catalyzed asymmetric domino reactions initiated by Michael additions has been successfully developed. The goal of this review is to collect the major developments in enantioselective nickel-catalyzed conjugate additions reported since the beginning of 2004, well illustrating the power of these inexpensive and highly abundant catalysts to achieve functionalized chiral compounds to be applied as key intermediates in the synthesis of biologically interesting molecules including natural products

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Section: Domino and Tandem Processes Initiated By A Michael Reactionmentioning

confidence: 99%

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

Pellissier

2015

Adv Synth Catal

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“…Amongst them, (E)-4-aryl-2-oxo-3-butenoates 1 have a specific advantage due to the presence of a further carbonyl group in the αЈ-position, because the 1,2dicarbonyl system may coordinate to a Lewis acid (Figure 1). Although certain reactions have been only occasionally investigated (e.g., alkylation, [1] hydrogenation, [2] and the aldol reaction [3] ), the classical Michael reaction has been extensively studied, [4,5] as has its oxa-, thio-, and Henry variants, [6][7][8] and tandem Michael-cyclization processes. ray crystal analysis.…”

Section: Introductionmentioning

confidence: 99%

The Asymmetric Formal Hetero‐Diels–Alder Reaction of Methyl (E)‐4‐Aryl‐2‐oxo‐3‐butenoates Catalyzed by [Sc(OTf)₃/pybox] Complexes

Desimoni¹,

Faita²,

Livieri³

et al. 2012

Eur J Org Chem

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The complex between scandium triflate and pybox is a good enantioselective catalyst for the reaction between methyl (E)‐4‐aryl‐2‐oxo‐3‐butenoates (1) and enol silyl ethers (2). The main products with (4′S)‐isopropyl‐, (4′S)‐phenyl‐, and (4′S,5′S)‐4‐TIPS‐pybox are methyl (4S,4aS,8aS)‐4‐aryl‐8a‐trialkylsiloxy‐hexahydro‐4H‐chromen‐2‐carboxylates (7), which are obtained in good yield and enantioselectivities of more than 95 % ee. Because the reaction gives products with a trans ring junction that cannot derive from a conventional concerted hetero‐Diels–Alder pathway, the mechanism involved in the enantioselective catalytic cycle and the origin of the stereoinduction were investigated. The structures of two desilylated products, 8b and 9b, were determined by X‐ray crystal analysis. Their absolute configuration was then related to that of 7 by stereospecific isomerization and/or desilylation reactions. If aryl‐butenoates 1 are coordinated to the catalyst, forming reacting complexes characterized by the five‐membered structure 11, these rigid reacting intermediates give a face discrimination that is determined by the configuration of the pybox 4′‐substituent. The resulting face‐selective attack of enol silyl ethers to coordinated 1 gives an enantioselective tandem Mukaiyama–Michael addition/intramolecular ring closure reaction, which is an enantioselective formal hetero‐Diels–Alder reaction, which rationalizes the absolute configuration of the reaction products.

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“…However, compared with α,β‐unsaturated ketones and nitroalkene, β,γ‐unsaturated α‐keto esters as Michael acceptors are limited 11. The asymmetric addition of 1,3‐difunctional donors to β,γ‐unsaturated‐α‐ketoesters catalyzed by organocatalysts11b–p and chiral metal catalysts based on copper,11r nickel,11s yttrium,11t and zinc11u has received intense attention, because the reaction can follow a domino acetalization to construct a chiral six‐membered oxygenated heterocycle. Retrosynthetically, a chiral five‐membered oxygen heterocycle can be formed through the reaction of β,γ‐unsaturated‐α‐ketoester with 1,2‐difunctional compound such as α‐hydroxyacetophenone, which has acted as donor in the Michael addition of α,β‐unsaturated ketones or nitroalkenes 12.…”

Section: Methodsmentioning

confidence: 99%

A New Strategy for Enantioselective Construction of Multisubstituted Five‐Membered Oxygen Heterocycles via a Domino Michael/Hemiketalization Reaction

Hua

Liu

Huang

et al. 2015

Chemistry A European J

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A new highly enantioselective domino Michael/hemiketalization reaction of α-hydroxyacetophenone with β,γ-unsaturated α-keto esters for the synthesis of 2,2,4,5-tetrasubstituted chiral tetrahydrofurans is reported. With 2 mol % intramolecular dinuclear zinc-AzePhenol complex prepared in situ from the reaction of multidentate semi-azacrown ether ligand with ZnEt2 , the corresponding anti-multisubstituted tetrahydrofuran products were obtained in up to 90 % yields, and 98 % enantiomeric excess (ee) at 0 °C for 45 min. Moreover, the products were easily converted to 2,3,5-trisubstituted 2,3-dihydrofurans without any loss in optical activity.

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N,N′-Dioxide–nickel(II) complex catalyzed asymmetric Michael addition of cyclic 1,3-dicarbonyl compounds to β,γ-unsaturated α-ketoesters

Cited by 52 publications

References 42 publications

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

The Asymmetric Formal Hetero‐Diels–Alder Reaction of Methyl (E)‐4‐Aryl‐2‐oxo‐3‐butenoates Catalyzed by [Sc(OTf)₃/pybox] Complexes

A New Strategy for Enantioselective Construction of Multisubstituted Five‐Membered Oxygen Heterocycles via a Domino Michael/Hemiketalization Reaction

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N,N′-Dioxide–nickel(II) complex catalyzed asymmetric Michael addition of cyclic 1,3-dicarbonyl compounds to β,γ-unsaturated α-ketoesters

Cited by 52 publications

References 42 publications

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

Recent Developments in Enantioselective Nickel(II)‐Catalyzed Conjugate Additions

The Asymmetric Formal Hetero‐Diels–Alder Reaction of Methyl (E)‐4‐Aryl‐2‐oxo‐3‐butenoates Catalyzed by [Sc(OTf)3/pybox] Complexes

A New Strategy for Enantioselective Construction of Multisubstituted Five‐Membered Oxygen Heterocycles via a Domino Michael/Hemiketalization Reaction

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The Asymmetric Formal Hetero‐Diels–Alder Reaction of Methyl (E)‐4‐Aryl‐2‐oxo‐3‐butenoates Catalyzed by [Sc(OTf)₃/pybox] Complexes