Discovery of a Formal Dyotropic Rearrangement during Acid-Mediated Dioxabicyclo[4.2.1]nonanone Formation

被引：0
|
作者：
Hashimoto, Yoshimitsu [1 ,2 ]
Kong, Wang-Yeuk [2 ]
Tantillo, Dean J. [2 ]
机构：
[1] Showa Pharmaceut Univ, Machida, Tokyo 1948543, Japan
[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
来源：
ORGANIC LETTERS | 2024年 / 26卷 / 26期
基金：
美国国家科学基金会;
关键词：
ADJUSTED PSEUDOPOTENTIALS; FRIEDEL-CRAFTS; ELEMENTS; MECHANISMS; ACIDITIES; SUPPORT; PATH;
D O I：
10.1021/acs.orglett.4c01616
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A new reaction mechanism for the construction of dioxabicyclo[4.2.1]nonanone skeletons via a cation cascade has been proposed and examined by DFT and ab initio computations. This mechanism features the following steps: (1) intramolecular Friedel-Crafts-type cyclization with a methyl oxocarbenium cation formed by carboxylate disconnection, (2) electron-rich aromatic ring assisted methoxide loss followed by lactone formation, and (3) stepwise dyotropic rearrangement resulting in skeletal isomerization from a dioxabicyclo[3.2.2]nonanone to the dioxabicyclo[4.2.1]nonanone product observed experimentally. The high regioselectivity and driving force for the overall rearrangement were rationalized, and Lewis and Br & oslash;nsted acid mediated reactivities were compared.
引用
收藏
页码：5441 / 5446
页数：6
相关论文
共 50 条
  • [31] Amino Acid-Mediated Formation of CO2 in Flash-Frozen Ceres Brines
    Vu, Tuan H.
    Reynoso, Lucas R.
    Johnson, Paul V.
    Hodyss, Robert
    ACS EARTH AND SPACE CHEMISTRY, 2024, 8 (06): : 1214 - 1223
  • [32] Acid-Mediated Formation of Soybean Isolate Protein Emulsion Gels with Soybean Oil as an Active Component
    Bi, Chonghao
    Zhou, Tong
    Wu, Zeyuan
    Huang, Zhigang
    FOODS, 2023, 12 (09)
  • [33] Acid-mediated formation of trifluoromethyl sulfonates from sulfonic acids and a hypervalent iodine trifluoromethylating agent
    Koller, Raffael
    Huchet, Quentin
    Battaglia, Philip
    Welch, Jan M.
    Togni, Antonio
    CHEMICAL COMMUNICATIONS, 2009, (40) : 5993 - 5995
  • [34] Bronsted Acid-Mediated Formal [3+3] Annulation Between Propargylic Alcohols and 1,3-Diketones
    Han, Ya-Ping
    Li, Xue-Song
    Zhu, Xin-Yu
    Sun, Zhou
    Li, Ming
    Wang, Yu-Zhao
    Liang, Yong-Min
    ADVANCED SYNTHESIS & CATALYSIS, 2018, 360 (05) : 870 - 874
  • [35] A Possible Path to Prebiotic Peptides Involving Silica and Hydroxy Acid-Mediated Amide Bond Formation
    McKee, Aaron D.
    Solano, Martin
    Saydjari, Andrew
    Bennett, Christopher J.
    Hud, Nicholas V.
    Orlando, Thomas M.
    CHEMBIOCHEM, 2018, 19 (18) : 1913 - 1917
  • [36] Tuning the Selectivity: Study of Solvent-Free Acid-Mediated Pinacolic-Pinacolone Rearrangement under Microwave Irradiation
    Billamboz, Muriel
    Banaszak, Estelle
    Rigo, Benoit
    CHEMISTRYSELECT, 2018, 3 (36): : 10236 - 10243
  • [37] Endosomal H2O2 production leads to localized cysteine sulfenic acid formation on proteins during lysophosphatidic acid-mediated cell signaling
    Klomsiri, Chananat
    Rogers, LeAnn C.
    Soito, Laura
    McCauley, Anita K.
    King, S. Bruce
    Nelson, Kimberly J.
    Poole, Leslie B.
    Daniel, Larry W.
    FREE RADICAL BIOLOGY AND MEDICINE, 2014, 71 : 49 - 60
  • [38] Fulvic Acid-Mediated Interfacial Reactions on Exposed Hematite Facets during Dissimilatory Iron Reduction
    Hu, Shiwen
    Wu, Yundang
    Li, Fangbai
    Shi, Zhenqing
    Ma, Chao
    Liu, Tongxu
    LANGMUIR, 2021, 37 (20) : 6139 - 6150
  • [39] Involvement of p38 MAPK phosphorylation and nitrate formation in aristolochic acid-mediated antiplatelet activity
    Shen, Ming-Yi
    Liu, Chien-Liang
    Hsiao, Geroge
    Liu, Chiung-Yueh
    Lin, Kuang-Hung
    Chou, Duen-Suey
    Sheu, Joen-Rong
    PLANTA MEDICA, 2008, 74 (10) : 1240 - 1245
  • [40] Trifluoroacetic Acid-Mediated Nucleophilic Substitution/Smiles Rearrangement Cascade Reaction: An Alternative Approach to Constructing Pyrrole-Fused Dihydropteridines
    Tong Zhu
    Jinbao Xiang
    Chemistry of Heterocyclic Compounds, 2016, 52 : 831 - 835
12345