Rhodium-catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from the Recent "gold Rush"

Overview

Journal Chem Soc Rev

Specialty Chemistry

Date 2012 Aug 17

PMID 22895533

Citations 27

Authors

Xing-Zhong Shu

Dongxu Shu

Casi M Schienebeck

Weiping Tang

Affiliations

Soon will be listed here.

Abstract

Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed.

Citing Articles

Selective transformation of propargylic ester towards tunable polymerization pathways.

Hu H, Duan X, Li M, Song W, Shi H, Wang G Nat Commun. 2025; 16(1):2160.

PMID: 40038290 PMC: 11880314. DOI: 10.1038/s41467-025-57619-7.

Regiodivergent Gold-Catalyzed Rearrangement-Addition Reactions of Sulfenylated Propargylic Carboxylates with Indoles.

More N, Rist P, Gupta A, Davies P Org Lett. 2024; 26(36):7713-7717.

PMID: 39207898 PMC: 11406574. DOI: 10.1021/acs.orglett.4c02853.

Copper-catalyzed propargylic C-H functionalization for allene syntheses.

Zhang D, Fan J, Shi Y, Huang Y, Fu C, Wu X Chem Sci. 2023; 14(34):9191-9196.

PMID: 37655026 PMC: 10466309. DOI: 10.1039/d3sc01501g.

Metal-free catalytic hydrocarboxylation of hexafluorobut-2-yne.

Zeng J, Zhao B, Tang X, Han S, Yang Z, Liu Z RSC Adv. 2022; 11(61):38938-38943.

PMID: 35493246 PMC: 9044190. DOI: 10.1039/d1ra06526b.

Gold-Catalyzed Synthesis of Small Rings.

Mato M, Franchino A, Garci A-Morales C, Echavarren A Chem Rev. 2020; 121(14):8613-8684.

PMID: 33136374 PMC: 8363095. DOI: 10.1021/acs.chemrev.0c00697.

References

Yao Z, Li J, Yu Z . Rh-catalyzed [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes and CO for the synthesis of cyclooctadienones. Org Lett. 2010; 13(1):134-7. DOI: 10.1021/ol102700m. View

Li X, Huang S, Schienebeck C, Shu D, Tang W . Rhodium-catalyzed carbonylation of 3-acyloxy-1,4-enynes for the synthesis of cyclopentenones. Org Lett. 2012; 14(6):1584-7. PMC: 3306479. DOI: 10.1021/ol300330t. View

Teng T, Liu R . Gold-catalyzed stereocontrolled oxacyclization/[4+2]-cycloaddition cascade of ketone-allene substrates. J Am Chem Soc. 2010; 132(27):9298-300. DOI: 10.1021/ja1043837. View

Marco-Contelles J, Soriano E . Recent developments in the metal-catalyzed reactions of metallocarbenoids from propargylic esters. Chemistry. 2007; 13(5):1350-7. DOI: 10.1002/chem.200601522. View

Zheng H, Zheng J, Yu B, Chen Q, Wang X, He Y . Pt-catalyzed tandem 1,2-acyloxy migration/intramolecular [3 + 2] cycloaddition of enynyl esters. J Am Chem Soc. 2010; 132(6):1788-9. DOI: 10.1021/ja910346m. View

Cai S, Liu Z, Zhang W, Zhao X, Wang D . Gold-catalyzed [3+2] cycloaddition/hydrolytic Michael addition/retro-aldol reactions of propargylic esters tethered to cyclohexadienones. Angew Chem Int Ed Engl. 2011; 50(47):11133-7. DOI: 10.1002/anie.201104028. View

Li X, Zhang M, Shu D, Robichaux P, Huang S, Tang W . Rhodium-catalyzed ring expansion of cyclopropanes to seven-membered rings by 1,5 C-C bond migration. Angew Chem Int Ed Engl. 2011; 50(44):10421-4. PMC: 3329940. DOI: 10.1002/anie.201104861. View

Gung B, Bailey L, Wonser J . Gold-catalyzed Intermolecular [4C + 3C] Cycloaddition Reactions. Tetrahedron Lett. 2010; 51(17):2251-2253. PMC: 2844647. DOI: 10.1016/j.tetlet.2010.02.099. View

Barluenga J, Riesgo L, Vicente R, Lopez L, Tomas M . Rearrangement of propargylic esters: metal-based stereospecific synthesis of (E)- and (Z)-knoevenagel derivatives. J Am Chem Soc. 2007; 129(25):7772-3. DOI: 10.1021/ja072864r. View

10.

Shapiro N, Shi Y, Toste F . Gold-catalyzed [3+3]-annulation of azomethine imines with propargyl esters. J Am Chem Soc. 2009; 131(33):11654-5. PMC: 2763378. DOI: 10.1021/ja903863b. View

11.

Shibata Y, Noguchi K, Tanaka K . Cationic rhodium(I) complex-catalyzed [3 + 2] and [2 + 1] cycloadditions of propargyl esters with electron-deficient alkynes and alkenes. J Am Chem Soc. 2010; 132(23):7896-8. DOI: 10.1021/ja102418h. View

12.

Gorin D, Watson I, Toste F . Fluorenes and styrenes by Au(I)-catalyzed annulation of enynes and alkynes. J Am Chem Soc. 2008; 130(12):3736-7. PMC: 2995287. DOI: 10.1021/ja710990d. View

13.

Lopez F, Mascarenas J . Recent developments in gold-catalyzed cycloaddition reactions. Beilstein J Org Chem. 2011; 7:1075-94. PMC: 3167873. DOI: 10.3762/bjoc.7.124. View

14.

Schwier T, Sromek A, Yap D, Chernyak D, Gevorgyan V . Mechanistically diverse copper-, silver-, and gold-catalyzed acyloxy and phosphatyloxy migrations: efficient synthesis of heterocycles via cascade migration/cycloisomerization approach. J Am Chem Soc. 2007; 129(32):9868-78. PMC: 2536635. DOI: 10.1021/ja072446m. View

15.

Watson I, Ritter S, Toste F . Asymmetric synthesis of medium-sized rings by intramolecular Au(I)-catalyzed cyclopropanation. J Am Chem Soc. 2009; 131(6):2056-7. PMC: 2662771. DOI: 10.1021/ja8085005. View

16.

Murakami M, Ubukata M, Itami K, Ito Y . Rhodium-Catalyzed Intermolecular [4+2] Cycloaddition of Unactivated Substrates. Angew Chem Int Ed Engl. 2018; 37(16):2248-2250. DOI: 10.1002/(SICI)1521-3773(19980904)37:16<2248::AID-ANIE2248>3.0.CO;2-1. View

17.

Zhang G, Catalano V, Zhang L . PtCl2-catalyzed rapid access to tetracyclic 2,3-indoline-fused cyclopentenes: reactivity divergent from cationic Au(I) catalysis and synthetic potential. J Am Chem Soc. 2007; 129(37):11358-9. DOI: 10.1021/ja074536x. View

18.

Murakami M, Itami K, Ubukata M, Tsuji I, Ito Y . Iridium-Catalyzed [5 + 1] Cycloaddition: Allenylcyclopropane as a Five-Carbon Assembling Unit. J Org Chem. 2001; 63(1):4-5. DOI: 10.1021/jo9718859. View

19.

Soriano E, Marco-Contelles J . New insights on the mechanism of the transition-metal stereoselective olefin cyclopropanation. Chemistry. 2008; 14(22):6771-9. DOI: 10.1002/chem.200800305. View

20.

Engel D, Dudley G . The Meyer-Schuster rearrangement for the synthesis of alpha,beta-unsaturated carbonyl compounds. Org Biomol Chem. 2009; 7(20):4149-58. DOI: 10.1039/b912099h. View