Trichloroisocyanuric Acid

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Mohammad Ali Zolfigol - One of the best experts on this subject based on the ideXlab platform.

Danfeng Huang - One of the best experts on this subject based on the ideXlab platform.

Hua Yang - One of the best experts on this subject based on the ideXlab platform.

  • enantiospecific total synthesis of tanikolide via a key 2 3 meisenheimer rearrangement with an allylic amine n oxide directed epoxidation and a one pot Trichloroisocyanuric Acid n debenzylation and n chlorination
    Journal of Organic Chemistry, 2013
    Co-Authors: Yangla Xie, Moran Sun, Hang Zhou, Qiwei Cao, Kaige Gao, Changling Niu, Hua Yang
    Abstract:

    The enantiospecific total synthesis of the δ-lactonic marine natural product (+)-tanikolide (1), isolated from Lyngbya majuscula , was achieved using a [2,3]-Meisenheimer rearrangement as the key reaction. During this rearrangement, we discovered that the allylic amine N-oxide could direct the m-CPBA double-bond epoxidation to the syn position. The resulting syn product 8 underwent epoxide ring opening under the m-CBA conditions to give the five- and six-membered cyclic ether amine N-oxides, which we further treated with Zn and conc. HCl to obtain the reduced bisbenzyl tertiary amines 23 and 22, respectively. When 23 and 22 were treated with Trichloroisocyanuric Acid (TCCA) in dichloromethane, oxidation at the benzyl position occurred, forming iminium ions. These intermediates were trapped by intramolecular reaction with the hydroxyls, and the resulting intermediates were then oxidized or shifted to afford 25 and 24, respectively. The entire one-pot process involves N-debenzylation, N-chlorination, and hemiacetal oxidation. The amine N-oxide-directed epoxidation complements Davies' ammonium-directed epoxidation. Thus, TCCA N-debenzylation is described for the first time and might be a useful N-debenzylation technique.

  • Enantiospecific Total Synthesis of (+)-Tanikolide via a Key [2,3]-Meisenheimer Rearrangement with an Allylic Amine N‑Oxide-Directed Epoxidation and a One-Pot Trichloroisocyanuric Acid N‑Debenzylation and N‑Chlorination
    2013
    Co-Authors: Yangla Xie, Moran Sun, Hang Zhou, Qiwei Cao, Kaige Gao, Changling Niu, Hua Yang
    Abstract:

    The enantiospecific total synthesis of the δ-lactonic marine natural product (+)-tanikolide (1), isolated from Lyngbya majuscula, was achieved using a [2,3]-Meisenheimer rearrangement as the key reaction. During this rearrangement, we discovered that the allylic amine N-oxide could direct the m-CPBA double-bond epoxidation to the syn position. The resulting syn product 8 underwent epoxide ring opening under the m-CBA conditions to give the five- and six-membered cyclic ether amine N-oxides, which we further treated with Zn and conc. HCl to obtain the reduced bisbenzyl tertiary amines 23 and 22, respectively. When 23 and 22 were treated with Trichloroisocyanuric Acid (TCCA) in dichloromethane, oxidation at the benzyl position occurred, forming iminium ions. These intermediates were trapped by intramolecular reaction with the hydroxyls, and the resulting intermediates were then oxidized or shifted to afford 25 and 24, respectively. The entire one-pot process involves N-debenzylation, N-chlorination, and hemiacetal oxidation. The amine N-oxide-directed epoxidation complements Davies’ ammonium-directed epoxidation. Thus, TCCA N-debenzylation is described for the first time and might be a useful N-debenzylation technique

Weigang Zhang - One of the best experts on this subject based on the ideXlab platform.

Bingbing Chang - One of the best experts on this subject based on the ideXlab platform.