Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization
Summary: Cooperative activation using halogen bonding and hydrogen bonding works in metal-catalyzed asymmetric halolactonization. The Zn3(OAc)4-3,3′-bis(aminoimino)binaphthoxide (tri-Zn) complex catalyzes both asymmetric iodolactonization and bromolactonization. Carboxylic acid substrates are conver...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2019-02-01
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| Series: | iScience |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2589004219300318 |
| _version_ | 1811228134908887040 |
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| author | Takayoshi Arai Kodai Horigane Ohji Watanabe Junki Kakino Noriyuki Sugiyama Hiroki Makino Yuto Kamei Shinnosuke Yabe Masahiro Yamanaka |
| author_facet | Takayoshi Arai Kodai Horigane Ohji Watanabe Junki Kakino Noriyuki Sugiyama Hiroki Makino Yuto Kamei Shinnosuke Yabe Masahiro Yamanaka |
| author_sort | Takayoshi Arai |
| collection | DOAJ |
| description | Summary: Cooperative activation using halogen bonding and hydrogen bonding works in metal-catalyzed asymmetric halolactonization. The Zn3(OAc)4-3,3′-bis(aminoimino)binaphthoxide (tri-Zn) complex catalyzes both asymmetric iodolactonization and bromolactonization. Carboxylic acid substrates are converted to zinc carboxylates on the tri-Zn complex, and the N-halosuccinimide (N-bromosuccinimide [NBS] or N-iodosuccinimide [NIS]) is activated by hydrogen bonding with the diamine unit of chiral ligand. Halolactonization is significantly enhanced by the addition of catalytic I2. Density functional theory calculations revealed that a catalytic amount of I2 mediates the alkene portion of the substrates and NIS to realize highly enantioselective iodolactonization. The tri-Zn catalyst activates both sides of the carboxylic acid and alkene moiety, so that asymmetric five-membered iodolactonization of prochiral diallyl acetic acids proceeded to afford the chiral γ-butyrolactones. In the total description of the catalytic cycle, iodolactonization using the NIS-I2 complex proceeds with the regeneration of I2, which enables the catalytic use of I2. The actual iodination reagent is I2 and not NIS. : Chemistry; Catalysis; Organic Synthesis; Stereochemistry Subject Areas: Chemistry, Catalysis, Organic Synthesis, Stereochemistry |
| first_indexed | 2024-04-12T09:53:27Z |
| format | Article |
| id | doaj.art-9502e03c9184489d9f24308a2c614ff2 |
| institution | Directory Open Access Journal |
| issn | 2589-0042 |
| language | English |
| last_indexed | 2024-04-12T09:53:27Z |
| publishDate | 2019-02-01 |
| publisher | Elsevier |
| record_format | Article |
| series | iScience |
| spelling | doaj.art-9502e03c9184489d9f24308a2c614ff22022-12-22T03:37:47ZengElsevieriScience2589-00422019-02-0112280292Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric HalolactonizationTakayoshi Arai0Kodai Horigane1Ohji Watanabe2Junki Kakino3Noriyuki Sugiyama4Hiroki Makino5Yuto Kamei6Shinnosuke Yabe7Masahiro Yamanaka8Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, Japan; Soft Molecular Activation Research Center (SMARC), Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, Japan; Chiba Iodine Research Innovation Center (CIRIC), 1-33 Yayoi, Inage, Chiba 263-8522, Japan; Corresponding authorDepartment of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, JapanDepartment of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, JapanDepartment of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, JapanDepartment of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, JapanDepartment of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba 263-8522, JapanDepartment of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8588, JapanDepartment of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8588, JapanDepartment of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8588, Japan; Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8588, Japan; Corresponding authorSummary: Cooperative activation using halogen bonding and hydrogen bonding works in metal-catalyzed asymmetric halolactonization. The Zn3(OAc)4-3,3′-bis(aminoimino)binaphthoxide (tri-Zn) complex catalyzes both asymmetric iodolactonization and bromolactonization. Carboxylic acid substrates are converted to zinc carboxylates on the tri-Zn complex, and the N-halosuccinimide (N-bromosuccinimide [NBS] or N-iodosuccinimide [NIS]) is activated by hydrogen bonding with the diamine unit of chiral ligand. Halolactonization is significantly enhanced by the addition of catalytic I2. Density functional theory calculations revealed that a catalytic amount of I2 mediates the alkene portion of the substrates and NIS to realize highly enantioselective iodolactonization. The tri-Zn catalyst activates both sides of the carboxylic acid and alkene moiety, so that asymmetric five-membered iodolactonization of prochiral diallyl acetic acids proceeded to afford the chiral γ-butyrolactones. In the total description of the catalytic cycle, iodolactonization using the NIS-I2 complex proceeds with the regeneration of I2, which enables the catalytic use of I2. The actual iodination reagent is I2 and not NIS. : Chemistry; Catalysis; Organic Synthesis; Stereochemistry Subject Areas: Chemistry, Catalysis, Organic Synthesis, Stereochemistryhttp://www.sciencedirect.com/science/article/pii/S2589004219300318 |
| spellingShingle | Takayoshi Arai Kodai Horigane Ohji Watanabe Junki Kakino Noriyuki Sugiyama Hiroki Makino Yuto Kamei Shinnosuke Yabe Masahiro Yamanaka Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization iScience |
| title | Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization |
| title_full | Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization |
| title_fullStr | Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization |
| title_full_unstemmed | Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization |
| title_short | Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization |
| title_sort | association of halogen bonding and hydrogen bonding in metal acetate catalyzed asymmetric halolactonization |
| url | http://www.sciencedirect.com/science/article/pii/S2589004219300318 |
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