Palladium-catalysed decarboxylative annulations of vinylethylene carbonates leading to diverse functionalised heterocycles.

Heterocycles are the fundamental structural motifs found in natural products and biologically active compounds. The construction of these structures is therefore an important task in organic chemistry. Vinylethylene carbonates (VECs) are versatile building blocks that can undergo transition metal catalysed decarboxylation to enable various kinds of interesting transformations. This review provides an overview of the significant achievements of VECs in palladium-catalysed annulations over the past five years. The flexible reactivity of VECs is demonstrated by various [3 + 2], [5 + n] and other types of annulations, which could offer powerful protocols for accessing diverse functionalised heterocycles.

[1]  Bo Han,et al.  Regiodivergent construction of medium-sized heterocycles from vinylethylene carbonates and allylidenemalononitriles† , 2020, Chemical science.

[2]  B. Trost,et al.  Annulative Allylic Alkylation Reactions Between Dual Electrophiles and Dual Nucleophiles: Applications in Complex Molecule Synthesis. , 2020, Chemistry.

[3]  J. Menéndez,et al.  Proline and its Derivatives as Organocatalysts for Multi‐ Component Reactions in Aqueous Media: Synergic Pathways to the Green Synthesis of Heterocycles , 2020, Advanced Synthesis and Catalysis.

[4]  M. Xie,et al.  Palladium-catalyzed asymmetric formal [3+2] cycloaddition of α-N-heterocyclic acrylates with vinyl epoxides for construction of isonucleoside analogs. , 2019, Chemical communications.

[5]  Rongli Zhang,et al.  Transition metal-catalyzed sp3 C-H activation and intramolecular C-N coupling to construct nitrogen heterocyclic scaffolds. , 2019, Chemical communications.

[6]  Xiu-qing Song,et al.  Formal [5+3] Cycloaddition of Vinylethylene Carbonates with Isatin‐Based α‐(Trifluoromethyl)imines for Diastereoselective Synthesis of Medium‐Heterocycle‐Fused Spirooxindoles , 2019, Advanced Synthesis & Catalysis.

[7]  Rong Zeng,et al.  Highly Chemo- and Diastereoselective Construction of Quaternary Stereocenters through Palladium-Catalyzed [3 + 2] Cyclization of 5-Alkenyl Thiazolones. , 2019, Organic letters.

[8]  B. Gabriele,et al.  Palladium-Catalyzed Double Cyclization Processes Leading to Polycyclic Heterocycles: Recent Advances , 2019, European Journal of Organic Chemistry.

[9]  Zhiqiang Zhang,et al.  Vinylethylene Carbonates as α,β-Unsaturated Aldehyde Surrogates for Regioselective [3 + 3] Cycloaddition. , 2019, Organic letters.

[10]  Yue Liu,et al.  Diastereoselective Construction of 6,8-Dioxabicyclo[3.2.1]octane Frameworks from Vinylethylene Carbonates via Palladium-Organo Relay Catalysis , 2019, ACS Catalysis.

[11]  M. Shi,et al.  Palladium-Catalyzed Diastereoselective Formal [5 + 3] Cycloaddition for the Construction of Spirooxindoles Fused with an Eight-Membered Ring. , 2019, Organic letters.

[12]  Qiao-Fei Bao,et al.  Ligand-controlled regiodivergent π-allyl palladium catalysis enables a switch between [3+2] and [3+3] cycloadditions. , 2019, Chemical communications.

[13]  S. Zlotin,et al.  Recent advances in the asymmetric synthesis of pharmacology-relevant nitrogen heterocycles via stereoselective aza-Michael reactions. , 2019, Organic & biomolecular chemistry.

[14]  Wei Sun,et al.  Enantioselective Synthesis of Chiral Medium-Sized Cyclic Compounds via Tandem Cycloaddition/Cope Rearrangement Strategy , 2019, ACS Catalysis.

[15]  W. Xiao,et al.  Enantioselective Trapping of Pd-Containing 1,5-Dipoles by Photogenerated Ketenes: Access to 7-Membered Lactones Bearing Chiral Quaternary Stereocenters. , 2018, Journal of the American Chemical Society.

[16]  Arjan W. Kleij,et al.  Catalytic nonreductive valorization of carbon dioxide into fine chemicals , 2019, Advances in Organometallic Chemistry.

[17]  Arjan W. Kleij,et al.  Diversity-Orientated Stereoselective Synthesis through Pd-Catalyzed Switchable Decarboxylative C-N/C-S Bond Formation in Allylic Surrogates. , 2018, Chemistry.

[18]  Sasa Wang,et al.  Pd-Catalyzed Umpolung of π–Allylpalladium Intermediates: Assembly of All-Carbon α-Vinyl Quaternary Aldehydes through C(sp3)–C(sp3) Coupling , 2018, ACS Catalysis.

[19]  Jiong Cheng,et al.  Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with β-Nitroolefins by Cooperative Catalysis of Palladium Complex and Squaramide , 2018, ACS Catalysis.

[20]  Weibo Yang,et al.  Divergent synthesis of N-heterocycles by Pd-catalyzed controllable cyclization of vinylethylene carbonates. , 2018, Chemical communications.

[21]  Arjan W. Kleij,et al.  Catalytic Transformations of Functionalized Cyclic Organic Carbonates. , 2018, Angewandte Chemie.

[22]  Xiu-qing Song,et al.  Formal [5+2] cycloaddition of vinylethylene carbonates to oxazol-5-(4H)-ones for the synthesis of 3,4-dihydrooxepin-2(7H)-ones. , 2018, Chemical communications.

[23]  Chang-Hua Ding,et al.  Palladium/ N-Heterocyclic Carbene (NHC)-Catalyzed Asymmetric [3 + 2] Cycloaddition Reaction of Vinyl Epoxides with Allenic Amides. , 2018, Organic letters.

[24]  Zi-Qiang Rong,et al.  Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis. , 2018, Angewandte Chemie.

[25]  Yong Jian Zhang,et al.  Pd-Catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones. , 2018, Chemical communications.

[26]  F. Glorius,et al.  Highly Enantioselective [5 + 2] Annulations through Cooperative N-Heterocyclic Carbene (NHC) Organocatalysis and Palladium Catalysis. , 2018, Journal of the American Chemical Society.

[27]  Z. Zhenhua,et al.  Formal [5+3] Cycloaddition of Zwitterionic Allylpalladium Intermediates with Azomethine Imines for Construction of N,O‐Containing Eight‐Membered Heterocycles , 2018 .

[28]  Arjan W. Kleij,et al.  A Domino Process toward Functionally Dense Quaternary Carbons through Pd-Catalyzed Decarboxylative C(sp3)-C(sp3) Bond Formation. , 2018, Journal of the American Chemical Society.

[29]  Y. Lan,et al.  Nine-Membered Benzofuran-Fused Heterocycles: Enantioselective Synthesis by Pd-Catalysis and Rearrangement via Transannular Bond Formation. , 2017, Journal of the American Chemical Society.

[30]  Ajmal Khan,et al.  Enantioselective Construction of Tertiary C-O Bond via Allylic Substitution of Vinylethylene Carbonates with Water and Alcohols. , 2017, Journal of the American Chemical Society.

[31]  W. Unsworth,et al.  Ring-Expansion Reactions in the Synthesis of Macrocycles and Medium-Sized Rings. , 2017, Chemistry.

[32]  D. Enders,et al.  Asymmetric organocatalytic methods for the synthesis of tetrahydropyrans and their application in total synthesis. , 2017, Chemical Society reviews.

[33]  Zi-Qiang Rong,et al.  Construction of Nine-Membered Heterocycles through Palladium-Catalyzed Formal [5+4] Cycloaddition. , 2017, Angewandte Chemie.

[34]  Q. Peng,et al.  Highly Diastereo- and Enantioselective Palladium-Catalyzed [3 + 2] Cycloaddition of Vinyl Epoxides and α,β-Unsaturated Ketones. , 2015, Organic letters.

[35]  Arjan W. Kleij,et al.  Palladium-Catalyzed Regio- and Enantioselective Synthesis of Allylic Amines Featuring Tetrasubstituted Tertiary Carbons. , 2016, Journal of the American Chemical Society.

[36]  Arjan W. Kleij,et al.  Highly Efficient Catalytic Formation of (Z)-1,4-But-2-ene Diols Using Water as a Nucleophile. , 2016, Angewandte Chemie.

[37]  Arjan W. Kleij,et al.  Stereoselective and Versatile Preparation of Tri- and Tetrasubstituted Allylic Amine Scaffolds under Mild Conditions. , 2016, Journal of the American Chemical Society.

[38]  Lei Yang,et al.  Pd-Catalyzed Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Imines. , 2015, Organic letters.

[39]  Wanbin Zhang,et al.  Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates. , 2015, Chemical Society reviews.

[40]  Wanbin Zhang,et al.  Palladium-catalyzed enantioselective decarboxylative cycloaddition of vinylethylene carbonates with isocyanates. , 2015, Chemistry.

[41]  Jing Xu,et al.  Palladium-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with Michael acceptors: construction of vicinal quaternary stereocenters. , 2014, Angewandte Chemie.

[42]  D. Mukherjee,et al.  Importance and synthesis of benzannulated medium-sized and macrocyclic rings (BMRs) , 2014 .

[43]  Y. Kan,et al.  Palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde: enantioselective construction of tertiary vinylglycols. , 2014, Angewandte Chemie.

[44]  P. Chiu,et al.  Vinyl epoxides in organic synthesis. , 2014, Chemical reviews.

[45]  T. Jamison,et al.  Recent progress in the synthesis of oxepanes and medium ring ethers , 2012 .

[46]  J. Weaver,et al.  Transition metal-catalyzed decarboxylative allylation and benzylation reactions. , 2011, Chemical reviews.

[47]  Isamu Shiina.  Total synthesis of natural 8- and 9-membered lactones: recent advancements in medium-sized ring formation. , 2007, Chemical reviews.

[48]  Yoshinori Yamamoto,et al.  Formation of cyclic ethers via the palladium-catalyzed cycloaddition of activated olefins with allylic carbonates having a hydroxy group at the terminus of the carbon chain. , 2001, The Journal of organic chemistry.

[49]  L. Yet.  Metal-mediated synthesis of medium-sized rings. , 2000, Chemical reviews.

[50]  Maier.  Synthesis of Medium-Sized Rings by the Ring-Closing Metathesis Reaction. , 2000, Angewandte Chemie.

[51]  Yoshinori Yamamoto,et al.  Palladium-Catalyzed Regioselective [3 + 2] Cycloaddition of Vinylic Oxiranes with Activated Olefins. A Facile Synthesis of Tetrahydrofuran Derivatives , 1998 .

[52]  B. Trost,et al.  Asymmetric Transition Metal-Catalyzed Allylic Alkylations. , 1996, Chemical reviews.

[53]  M. Shiro,et al.  Regio- and Stereoselective Synthesis of 1,3-Hydroxyl Amines via Palladium-Catalyzed Carbonate-Carbamate Transformation with Unique Stereoselectivity: Synthesis of 3-Amino-4-penten-1-ols , 1994 .

[54]  B. Trost,et al.  Regioselective joining of prenyl units. A simple strategy for geometry control in Pd catalyzed allylic alkylations , 1991 .

[55]  Z. Yoshida,et al.  Synthesis of 2-vinyl-γ-butyrolactones by the palladium-catalyzed decarboxylative carbonylation of 3-vinyl-1-oxo-2,6-dioxacyclohexanes , 1987 .

[56]  B. Trost.  New rules of selectivity: allylic alkylations catalyzed by palladium , 1980 .

[57]  B. Trost,et al.  New conjunctive reagents. 2-Acetoxymethyl-3-allyltrimethylsilane for methylenecyclopentane annulations catalyzed by palladium(0) , 1979 .

[58]  B. Trost,et al.  New synthetic reactions. Allylic alkylation , 1973 .

[59]  J. Tsuji,et al.  Organic syntheses by means of noble metal compounds XVII. Reaction of π-allylpalladium chloride with nucleophiles☆ , 1965 .

[60]  J. Tsuji,et al.  Organic Syntheses by Means of Noble Metal Compounds. VIII.1 Catalytic Carbonylation of Allylic Compounds with Palladium Chloride , 1964 .