Development of Synthetic Organic Reaction through the Formation of Halocyclization Intermediate as an Activating Method

Osamu Kitagawa, Takeo Taguchi

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We report here the results of synthetic organic reactions which proceed under mild conditions through the formation of cationic halocyclization intermediates. In the presence of I2 and collidine or lutidine, α-iodination reactions of unsaturated carboxamides and N-allylic carboxamides proceed in good yields through the activation of α-hydrogens by the formation of cyclic iminium ethers (iodolactonization intermediates). The iodine-mediated method can be also applied to the activation of enamide derivatives; that is, in the presence of I2, the Diels-Alder reactions of N-allylic enamides which are unreactive dienophiles, proceed in good yield through the formation of the cyclic iminium ether. These activation processes are successfully extended to asymmetric α-iodination of unsaturated carboxamides having homochiral 2,5-disubstituted pyrrolidine and asymmetric Diels-Alder reaction using novel axially chiral N-acryl anilide. Furthermore, the reactions of p-methoxybenzyl pentenyl ether with NIS and O-pentenyl oxime with NBS resulted in the activation of C-O bond and N-O bond through the formation of cationic haloetherification intermediates, and the following reaction with alchols and migration of anti-substituent gave p-methoxybenzylation and Beckmann rearrangement products in good yields, respectively.

Original languageEnglish
Pages (from-to)661-671
Number of pages11
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume56
Issue number8
Publication statusPublished - 1998
Externally publishedYes

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Chemical activation
Ether
Anilides
Oximes
Ethers
Iodine
Hydrogen
Derivatives

Keywords

  • α-iodination
  • Asymmetric reaction
  • Axially chiral anilide
  • Beckmann rearrangement
  • Diels-alder reaction
  • Halocyclization intermediate
  • Iodine
  • N-Bromosuccinimide (NBS)
  • N-Iodosuccinimide (NIS)
  • p-Methoxybenzyiation

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Development of Synthetic Organic Reaction through the Formation of Halocyclization Intermediate as an Activating Method",
abstract = "We report here the results of synthetic organic reactions which proceed under mild conditions through the formation of cationic halocyclization intermediates. In the presence of I2 and collidine or lutidine, α-iodination reactions of unsaturated carboxamides and N-allylic carboxamides proceed in good yields through the activation of α-hydrogens by the formation of cyclic iminium ethers (iodolactonization intermediates). The iodine-mediated method can be also applied to the activation of enamide derivatives; that is, in the presence of I2, the Diels-Alder reactions of N-allylic enamides which are unreactive dienophiles, proceed in good yield through the formation of the cyclic iminium ether. These activation processes are successfully extended to asymmetric α-iodination of unsaturated carboxamides having homochiral 2,5-disubstituted pyrrolidine and asymmetric Diels-Alder reaction using novel axially chiral N-acryl anilide. Furthermore, the reactions of p-methoxybenzyl pentenyl ether with NIS and O-pentenyl oxime with NBS resulted in the activation of C-O bond and N-O bond through the formation of cationic haloetherification intermediates, and the following reaction with alchols and migration of anti-substituent gave p-methoxybenzylation and Beckmann rearrangement products in good yields, respectively.",
keywords = "α-iodination, Asymmetric reaction, Axially chiral anilide, Beckmann rearrangement, Diels-alder reaction, Halocyclization intermediate, Iodine, N-Bromosuccinimide (NBS), N-Iodosuccinimide (NIS), p-Methoxybenzyiation",
author = "Osamu Kitagawa and Takeo Taguchi",
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T1 - Development of Synthetic Organic Reaction through the Formation of Halocyclization Intermediate as an Activating Method

AU - Kitagawa, Osamu

AU - Taguchi, Takeo

PY - 1998

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N2 - We report here the results of synthetic organic reactions which proceed under mild conditions through the formation of cationic halocyclization intermediates. In the presence of I2 and collidine or lutidine, α-iodination reactions of unsaturated carboxamides and N-allylic carboxamides proceed in good yields through the activation of α-hydrogens by the formation of cyclic iminium ethers (iodolactonization intermediates). The iodine-mediated method can be also applied to the activation of enamide derivatives; that is, in the presence of I2, the Diels-Alder reactions of N-allylic enamides which are unreactive dienophiles, proceed in good yield through the formation of the cyclic iminium ether. These activation processes are successfully extended to asymmetric α-iodination of unsaturated carboxamides having homochiral 2,5-disubstituted pyrrolidine and asymmetric Diels-Alder reaction using novel axially chiral N-acryl anilide. Furthermore, the reactions of p-methoxybenzyl pentenyl ether with NIS and O-pentenyl oxime with NBS resulted in the activation of C-O bond and N-O bond through the formation of cationic haloetherification intermediates, and the following reaction with alchols and migration of anti-substituent gave p-methoxybenzylation and Beckmann rearrangement products in good yields, respectively.

AB - We report here the results of synthetic organic reactions which proceed under mild conditions through the formation of cationic halocyclization intermediates. In the presence of I2 and collidine or lutidine, α-iodination reactions of unsaturated carboxamides and N-allylic carboxamides proceed in good yields through the activation of α-hydrogens by the formation of cyclic iminium ethers (iodolactonization intermediates). The iodine-mediated method can be also applied to the activation of enamide derivatives; that is, in the presence of I2, the Diels-Alder reactions of N-allylic enamides which are unreactive dienophiles, proceed in good yield through the formation of the cyclic iminium ether. These activation processes are successfully extended to asymmetric α-iodination of unsaturated carboxamides having homochiral 2,5-disubstituted pyrrolidine and asymmetric Diels-Alder reaction using novel axially chiral N-acryl anilide. Furthermore, the reactions of p-methoxybenzyl pentenyl ether with NIS and O-pentenyl oxime with NBS resulted in the activation of C-O bond and N-O bond through the formation of cationic haloetherification intermediates, and the following reaction with alchols and migration of anti-substituent gave p-methoxybenzylation and Beckmann rearrangement products in good yields, respectively.

KW - α-iodination

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KW - Axially chiral anilide

KW - Beckmann rearrangement

KW - Diels-alder reaction

KW - Halocyclization intermediate

KW - Iodine

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KW - N-Iodosuccinimide (NIS)

KW - p-Methoxybenzyiation

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