Interception of a Rautenstrauch Intermediate by Alkynes for [5+2] Cycloaddition: Rhodium‐Catalyzed Cycloisomerization of 3‐Acyloxy‐4‐ene‐1,9‐diynes to Bicyclo[5.3.0]decatrienes

Shu, Xing‐Zhong; Huang, Shih-Chien; Shu, Dongxu; Guzei, Ilia A.; Tang, Weiping

doi:10.1002/ange.201103136

Cited by 53 publications

(19 citation statements)

References 98 publications

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“…[18,19] When a mixture of the propargylic ether 1a and diene 3a was treated with this catalyst at 80°C, no reaction occurred (Table 1, entry 1). We have previously found that electron-deficient phosphine or phosphite ligands often increase the acidity of rhodium catalysts and promote 1,2-acyloxy [20] or 1,3-acyloxy [19] migration of propargylic esters. Indeed, a mixture of the [4+3] cycloaddition product 4a and simple indole 7 was observed when 1a was treated with [{Rh(CO) 2 Cl} 2 ] in the presence of such ligands (entries 2–4).…”

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Rhodium‐ and Platinum‐Catalyzed [4+3] Cycloaddition with Concomitant Indole Annulation: Synthesis of Cyclohepta[b]indoles

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Rhodium‐ and Platinum‐Catalyzed [4+3] Cycloaddition with Concomitant Indole Annulation: Synthesis of Cyclohepta[b]indoles

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“…(1)]. [6] Afterwords, the more challenging intermoelcuarl version of this cycloaddition was also realized for the synthesis of achiral mono-cyclic seven-memberd rings. [7] Prior to our study, vinylcyclopropane has been the only 5-carbon building block developed for transtion metal-catalyzed intramolecular [8] and intermolecular [9] (5+2) cycloadditions.…”

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“…However, we found that while Rh(I) catalysts were very effective in promoting the intramolecular (5+2) cycloaddition of ACEs with alkynes, gold and other transition metals did not provide any desired cycloaddition product. [6,7] The centre-to-helix-to-centre chirality transfer mechanism proposed for Au-catalyst [14] is not necessarily applicable to Rh I -catalyzed (5+2) cycloadditions.…”

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“…[18] We have previously demonstrated that electron-withdrawing group could facilitate the 1,2-acyloxy migration in Rh-catalyzed intramolecular [6] and intermolecular [7] (5+2) cycloaddition of ACEs. The corresponding chiral alcohols for substrates 1e – 1g were prepared from dinuclear Zn-catalyzed asymmetric addition of ethyl propiolate to α,β-unsaturated aldehydes developed by Trost group.…”

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“…1i ). [6] On the other hand, phosphite ligands are detrimental to the efficiency of the chirality transfer (entries 5 and 6, Table 1). We were pleased to find that a synthetically useful 84% ee could be obtained for product 2i (entry 10).…”

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Transfer of Chirality in the Rhodium‐Catalyzed Intramolecular [5+2] Cycloaddition of 3‐Acyloxy‐1,4‐enynes (ACEs) and Alkynes: Synthesis of Enantioenriched Bicyclo[5.3.0]decatrienes

et al. 2013

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Chiral Bicyclic Bicyclo[5.3.0]decatrienes were prepared enantioselectively for the first time from readily available chiral 3-acyloxy-1,4-enynes (ACEs). The chirality of the allylic/propargylic esters in ACEs could be transferred with high efficiency to the bicyclic products in most cases. The experimentally observed overall inversion of stereochemistry confirmed the prediction from previous computational studies.

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Recent Developments in The [5+2] Cycloaddition

Clavier¹,

Pellissier²

2014

Methods and Applications of Cycloaddition Reactions in Organic Syntheses

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The [5+2] cycloaddition allows the synthesis of a diversity of complex highly functionalized seven-membered products in a single step. These cycloadducts can readily be further manipulated synthetically for use in the synthesis of a number of complex natural products and important biologically active products containing seven-membered rings. In addition to the common and highly efficient [5+2] cycloadditions of (oxido)pyrylium and (oxido)pyridinium ions with various p-systems, providing an easy access to a wide range of novel heterocyclic sevenmembered rings exhibiting an oxygen or nitrogen bridge, the metal-catalyzed [5+2] cycloadditions still attract a great attention and have become one of the most popular ways of constructing seven-membered compounds. Among the most important reactions are metal-catalyzed (hetero) [5+2] cycloadditions of vinyl-substituted three-membered rings, rhodium-catalyzed [5+2] cycloadditions of 3-acyloxy-1,4-enynes, and metal-catalyzed [5+2] cycloadditions of ortho-vinylphenols and ortho-vinyl/arylanilines. Scheme 1. The metal-catalyzed [5+2] cycloaddition of vinylcyclopropanes and possible mechanisms.Scheme 2. First examples of rhodium-catalyzed intermolecular [5+ +2] cycloadditions of vinylcyclopropanes.Scheme 3. The [5+2] cycloaddition of a vinylcyclopropane and propargyltrimethylsilanes catalyzed with [Rh(C 10 H 8 )(cod)] + SbF 6 À and a tandem [5+ +2] cycloaddition/ protodesilylation reaction. Scheme 4. Three-component domino/tandem [5+2] cycloaddition/vinylogous Peterson/[4+2] cycloaddition reactions of a vinylcyclopropane, 4-(trimethylsilyl)but-2-yn-1-ol and alkenes/alkynes catalyzed with [Rh(Naph)(cod)] + SbF 6 À . Scheme 5. The [5+2] cycloaddition of a vinylcyclopropane and a dimethylalleneyne catalyzed with [Rh(CO) 2 Cl] 2 . Scheme 6. Iridium-catalyzed [5+2] cycloadditions of vinylcyclopropanes and alkynes. Scheme 7. First examples of rhodium-catalyzed intramolecular [5+2] cycloadditions of vinylcyclopropanes with various p-systems. Scheme 8. Intramolecular [5+2] cycloaddition of vinylcyclopropanes and alkynes catalyzed with [{Ir(dbcot)Cl} 2 ]. Scheme 14. Rhodium-catalyzed intramolecular hetero [5+2] cycloaddition of vinyloxiranes and alkynes. Scheme 25. Dearomative indole [5+2] cycloadditions of oxidopyrylium ions and alkenes. Scheme 26. Type 2 [5+2] cycloadditions of oxidopyrylium ions and alkenes or alkyne. Scheme 45. Scandium-catalyzed [5+2] cycloaddition of N-indolyl alkylidene b-amide esters and alkenes. Scheme 51. Rhodium-catalyzed domino [3+2] cycloaddition/[5+2] cycloaddition reactions of 4-aryl-1,2,3-triazoles and internal alkynes.

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Interception of a Rautenstrauch Intermediate by Alkynes for [5+2] Cycloaddition: Rhodium‐Catalyzed Cycloisomerization of 3‐Acyloxy‐4‐ene‐1,9‐diynes to Bicyclo[5.3.0]decatrienes

Cited by 53 publications

References 98 publications

Rhodium‐ and Platinum‐Catalyzed [4+3] Cycloaddition with Concomitant Indole Annulation: Synthesis of Cyclohepta[b]indoles

Rhodium‐ and Platinum‐Catalyzed [4+3] Cycloaddition with Concomitant Indole Annulation: Synthesis of Cyclohepta[b]indoles

Transfer of Chirality in the Rhodium‐Catalyzed Intramolecular [5+2] Cycloaddition of 3‐Acyloxy‐1,4‐enynes (ACEs) and Alkynes: Synthesis of Enantioenriched Bicyclo[5.3.0]decatrienes

Recent Developments in The [5+2] Cycloaddition

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