Highly Efficient Rhodium-Catalyzed Asymmetric Ring-Opening Reactions of Oxabenzonorbornadiene with Amine Nucleophiles

Long, Yuhua; Zhao, Shuang-Qi; Zeng, Heping; Yang, Dingqiao

doi:10.1007/s10562-010-0383-3

Cited by 20 publications

(4 citation statements)

References 18 publications

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“…The Lautens group pioneered the study of asymmetric ring-opening (ARO) of oxabicyclic compounds [ 12 ], and since then, a lot of work has been done to study the reactivity of OBDs, namely using different transition metal-catalysts with various nucleophiles. Transition metal-catalysts, which have been used in ring-opening reactions of OBD, include Cu [ 13 , 14 ], Fe [ 15 ], Ir [ 16 ], Ni [ 17 , 18 ], Pd [ 19 , 20 ], Pt [ 21 - 23 ], Rh [ 24 , 25 ], Ru [ 26 , 27 ], and Zr [ 28 ]. The goal of these ring h4-opening reactions is to construct new carbon-heteroatom or carbon-carbon bonds within the dihydronaphthalene framework.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Boutin

Koh

Tam

2019

COS

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Background: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate capable of undergoing multiple types of transformations due to three key structural features: a free alkene, a bridged oxygen atom, and a highly strained ring system. Most notably, ring-opening reactions of OBD using transition metal catalysts and nucleophiles produce multiple stereocenters in a single step. The resulting dihydronaphthalene framework is found in many natural products, which have been shown to be biologically active. Objective: This review will provide an overview of transition metal-catalyzed reactions from the past couple of years including cobalt, copper, iridium, nickel, palladium and rhodium- catalyzed reactions. In addition, the recent derivatization of OBD to cyclopropanated oxabenzonorbornadiene and its reactivity will be discussed. Conclusion: It can be seen from the review, that the work done on this topic has employed the use of many different transition metal catalysts, with many different nucleophiles, to perform various transformations on the OBD molecule. Additionally, depending on the catalyst and ligand used, the stereo and regioselectivity of the product can be controlled, with proposed mechanisms to support the understanding of such reactions. The use of palladium has also generated a cyclopropanated OBD, with reactivity similar to that of OBD. An additional reactive site exists at the distal cyclopropane carbon, giving rise to three types of ring-opened products.

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Section: Introductionmentioning

confidence: 99%

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Boutin

Koh

Tam

2019

COS

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“…The use of oxabicyclic templates to introduce trans- 1,2-bifunctional groups to the carbocyclic molecule skeleton is an effective strategy for the synthesis of complex molecules. Pioneering work in this field was first described by Lautens and co-workers [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17] who reported rhodium-catalyzed asymmetric ring-opening (ARO) of oxabicyclic alkenes to produce the corresponding products in high yields and excellent enantioselectivities (up to 99% ee ). The asymmetric ring-opening has been extensively studied with a broad range of nucleophiles, including organomagnesium, organolithium, organozinc reagents, organoboronic acids, alcohols, phenols, carboxylic acids, terminal alkynes, and aromatic amines.…”

Section: Introductionmentioning

confidence: 99%

Iridium-Catalyzed Asymmetric Ring-Opening of Oxabenzonorbornadienes with N-Substituted Piperazine Nucleophiles

2015

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Iridium-catalyzed asymmetric ring-opening of oxabenzonorbornadienes with N-substituted piperazines was described. The reaction afforded the corresponding ring-opening products in high yields and moderate enantioselectivities in the presence of 2.5 mol % [Ir(COD)Cl] 2 and 5.0 mol % (S)-p-Tol-BINAP. The effects of various chiral bidentate ligands, catalyst loading, solvent, and temperature on the yield and enantioselectivity were also investigated. A plausible mechanism was proposed to account for the formation of the corresponding trans-ring opened products based on the X-ray structure of product 2i.

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“…For example, they are often used to construct substituted tetrahydronaphthalene skeletons in the presence of metal catalysts such as Pd [9–10], Ir [11–15], Rh [16–21] and Cu [22]. However, their reactivity in the presence of gold catalysts has been rarely reported [23].…”

Section: Introductionmentioning

confidence: 99%

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives

Sun¹,

Xu²,

Shi³

2013

Beilstein J. Org. Chem.

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SummaryOxabicyclic alkenes can react with electron-deficient terminal alkynes in the presence of a gold catalyst under mild conditions, affording the corresponding addition products in moderate yields. When using alkynyl esters as substrates, the (Z)-acrylate derivatives are obtained. Using but-3-yn-2-one (ethynyl ketone) as a substrate, the corresponding addition product is obtained with (E)-configuration. The proposed mechanism of these reactions is also discussed.

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Highly Efficient Rhodium-Catalyzed Asymmetric Ring-Opening Reactions of Oxabenzonorbornadiene with Amine Nucleophiles

Cited by 20 publications

References 18 publications

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Iridium-Catalyzed Asymmetric Ring-Opening of Oxabenzonorbornadienes with N-Substituted Piperazine Nucleophiles

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives

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