Bimetallic Rhodium(II)/Indium(III) Relay Catalysis for Tandem Insertion/Asymmetric Claisen Rearrangement

Chen, Yushuang; Dong, Shujuan; Xu, Xi; Liu, Xiaohua; Feng, Xiaoming

doi:10.1002/ange.201810410

Cited by 21 publications

(3 citation statements)

References 76 publications

(17 reference statements)

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“…In the absence of AuCl∙PPh 3 /AgOTf or In(OTf) 3 / L-PiEt 2 Me , only trace amount of the product 3aa was detected, which indicates that the two catalysts work cooperatively. N , Nʹ -dioxide/In(OTf) 3 crystal structure obtained in our previous study 49 showed that a OH-bridged dinuclear indium complex forms in the presence of H 2 O, in which N , Nʹ -dioxide coordinates to In(III) in a tetradentate manner. Nevertheless, the investigation of relationship between the e.e.…”

Section: Resultsmentioning

confidence: 93%

Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,Nʹ-dioxide-indium(III) or nickel(II) synergistic catalysis

Tang

Zhang

et al. 2021

Nat Commun

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Intermolecular addition of enols and enolates to unactivated alkynes was proved to be a simple and powerful method for carbon-carbon bond formation. Up to date, a catalytic asymmetric version of alkyne with 1,3-dicarbonyl compound has not been realized. Herein, we achieve the catalytic asymmetric intermolecular addition of 1,3-dicarbonyl compounds to unactivated 1-alkynes attributing to the synergistic activation of chiral N,N′-dioxide-indium(III) or nickel(II) Lewis acid and achiral gold(I) π-acid. A range of β-ketoamides, β-ketoesters and 1,3-diketones transform to the corresponding products with a tetra-substituted chiral center in good yields with good e.r. values. Besides, a possible catalytic cycle and a transition state model are proposed to illustrate the reaction process and the origin of chiral induction based on the experimental investigations.

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Section: Resultsmentioning

confidence: 93%

Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,Nʹ-dioxide-indium(III) or nickel(II) synergistic catalysis

Tang

Zhang

et al. 2021

Nat Commun

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“…On the basis of the mechanism of transition-metalcatalyzed enyne cycloisomerization, [7] our previous works, [10] and the determination of the absolute configuration of the products, [14] stereocontrol models for the [4+ +2] cycloaddition steps were proposed (Figure 1). Thec hiral N,N'-dioxide ligands coordinate to the Sc III or Ni II center in atetradentate manner to form octahedral structures.I nt he former case, chalcone 2 coordinates to the N,N'-dioxide-Sc III catalyst in amonodentate manner.T he catalyst activates the dienophile by decreasing the LUMO energy.S ubsequently,d ue to the steric hindrance of amide group of the ligand, the 1-methyl-2,3-disubstituted diene B could attack from b-Si face of a,bunsaturated ketone to form (4S,5 S,6 S)-3a ( Figure 1A).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[9] Recently,c hiral N,N'-dioxide-metal complex catalysts have proved to be good partners with several transition metals in relay catalysis. [10] Inspired by these works,weset out to combine the regiodiversity of 1,6-enyne cycloisomerization with the efficient enantioselection of chiral asymmetric Diels-Alder reactions catalyzed by N,N'-dioxide-metal complexes (Scheme 1B). In our proposal, different diene partners (B, D, and F)a re available in the presence of unique transitionmetal salts to perform the sequential [4+ +2] cycloadditions.…”

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confidence: 99%

Diversified Cycloisomerization/Diels–Alder Reactions of 1,6‐Enynes through Bimetallic Relay Asymmetric Catalysis

Zheng

Wang

et al. 2019

Angewandte Chemie

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We report the combination of transition-metalcatalyzedd iversified cycloisomerization of 1,6-enynes with chiral Lewis acid promoted asymmetric Diels-Alder reaction to realizea symmetric cycloisomerization/Diels-Alder relay reactions of 1,6-enynes with electron-deficient alkenes.Abroad spectrum of chiral [5,6]-bicyclic products could be acquired in high yields (up to 99 %) with excellent diastereoselectivy (> 19:1 dr) and enantioselectivity (up to 99 %ee).Diversified synthesis is one of the fundamental abilities of biosystems and plays as ignificant role in biological evolution. [1] Inspired by naturess trategy,m any efforts have been devoted to the development of diversified synthesis to afford two or more different types of products with stereochemical or scaffold selectivity from an identical set of starting materials under readily tunable conditions. [2] Theu se of dual-catalyst-promoted asymmetric tandem reactions (Scheme 1A), [3] which improves the synthetic efficiency and reduces waste generation, is an "expected" strategy to achieve switchable stereochemical synthesis through independent control of different catalyst cycles.I np articular,t he combination of metal catalysis with organocatalysis has produced great achievements. [4] Comparatively,t he combination of metal catalysis with Lewis acid catalysis (bimetallic) is more difficult and less developed, [5] due to the possible challenges that two distinct metals might competitively coordinate with the ligand, as well as potentially affection each other's catalytic cycles.Enynes are the most common synthons in sesquiterpene synthesis.S ince the seminal work of B. M. Tr ost et al., [6] metal-catalyzed 1,n-enyne cycloisomerization has become one of the most atom-economic strategies for the synthesis of functionalized carbo-or heterocycles in natural product synthesis. [7] Intriguingly,v arious conjugated 1,3-dienes or unconjugated 1,4-dienes could be obtained through different reaction pathways by adjusting the catalyst and reaction conditions.T he regiodiversity of metal-catalyzed 1,n-enyne cycloisomerization provides the possibility to realize asymmetric diversified synthesis.I np articular,t andem cycloiso-merization/Diels-Alder reaction of enynes with alkenes or aldehydes can produce useful [5,6]-bicyclic skeletons. [8] Nevertheless,c atalytic asymmetric versions to synthesize chiral [5,6]-bicyclic skeletons are still rare.O nly Andersonsg roup has reported an asymmetric cycloisomerization/Diels-Alder reaction of pyrrolidinyl dienals with electron-deficient alkenes by combining palladium catalysis and trienamine catalysis. [9] Recently,c hiral N,N'-dioxide-metal complex catalysts have proved to be good partners with several transition metals in relay catalysis. [10] Inspired by these works,weset out to combine the regiodiversity of 1,6-enyne cycloisomerization with the efficient enantioselection of chiral asymmetric Diels-Alder reactions catalyzed by N,N'-dioxide-metal complexes (Scheme 1B). In our proposal, different diene partners (B, D, and F)a re a...

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Synthesis of α‐(2‐Hydroxyphenyl)‐α‐Aminoketones by Rhodium‐Catalyzed Tandem Reaction of 1‐Sulfonyl‐1,2,3‐Triazoles and Benzoquinone‐Derived Alcohols

Wang

Cen

et al. 2020

Adv Synth Catal

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Readily available 1‐sulfonyl‐1,2,3‐triazole and benzoquinone‐derived alcohols were employed in a synthesis protocol for the formation of α‐(2‐hydroxyphenyl)‐α‐aminoketone. The cascade reaction includes the formation of rhodium carbene, O−H bond 1,3‐insertion, Claisen rearrangement as well as aromatization. Valuable benzoxazinone and 3‐aminobenzofuran were obtained after one‐step derivatization. Moreover, an estrone derivative was modified via the protocol with extraordinary efficiency.magnified image

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Bimetallic Rhodium(II)/Indium(III) Relay Catalysis for Tandem Insertion/Asymmetric Claisen Rearrangement

Cited by 21 publications

References 76 publications

Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,Nʹ-dioxide-indium(III) or nickel(II) synergistic catalysis

Catalytic asymmetric Nakamura reaction by gold(I)/chiral N,Nʹ-dioxide-indium(III) or nickel(II) synergistic catalysis

Diversified Cycloisomerization/Diels–Alder Reactions of 1,6‐Enynes through Bimetallic Relay Asymmetric Catalysis

Synthesis of α‐(2‐Hydroxyphenyl)‐α‐Aminoketones by Rhodium‐Catalyzed Tandem Reaction of 1‐Sulfonyl‐1,2,3‐Triazoles and Benzoquinone‐Derived Alcohols

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