Novel synthesis of alkenes via triethylborane-induced free-radical reactions of alkyl iodides and β-nitrostyrenes

J. T. Liu, Y. J. Jang, Y. K. Shih, S. R. Hu, C. M. Chu, C. F. Yao

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Abstract

Reactions of (E)-β-nitrostyrenes 1 and triethylborane 2 or tricyclohexylborane 4 in THF solution at room temperature in the presence of oxygen in the air as radical initiator generate high yields of trans-alkenes (E)-3 or (E)-5. Medium to high yields of different (E)-alkenes (E)-5, 7, 10, 12, and 14 also can be prepared when 1 reacts with different radicals, prepared from secondary alkyl iodides 6 and 8 or tertiary alkyl iodides 9, 11, and 13, in the presence of 2 and air as radical initiator. The generation of the only product (E)-alkenes can be explained by the generation of the benzylic radical A and/or B as the intermediate only and the mechanism is similar to Scheme 1. Both (E)- and (Z)-16a-c are generated when (E)- and (Z)-15a-c are used to react with adamantyl radical under similar conditions. Only (Z)-16d was observed when either (E)- or (Z)-15d was used to react with adamantyl radical. The generation of the (E)- and/or (Z)-alkenes can be explained by the free rotation of the A and/or B to generate A′ and/or B′ and vice versa, and the mechanism is proposed to be a free-radical reaction via NO2/alkyl substitution and is shown as Scheme 2.

Original languageEnglish
Pages (from-to)6021-6028
Number of pages8
JournalJournal of Organic Chemistry
Volume66
Issue number18
DOIs
Publication statusPublished - 2001 Sep 7

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Free radical reactions
Alkenes
Iodides
Free Radicals
Air
Substitution reactions
Oxygen
Temperature
triethylborane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Novel synthesis of alkenes via triethylborane-induced free-radical reactions of alkyl iodides and β-nitrostyrenes. / Liu, J. T.; Jang, Y. J.; Shih, Y. K.; Hu, S. R.; Chu, C. M.; Yao, C. F.

In: Journal of Organic Chemistry, Vol. 66, No. 18, 07.09.2001, p. 6021-6028.

Research output: Contribution to journalArticle

Liu, J. T. ; Jang, Y. J. ; Shih, Y. K. ; Hu, S. R. ; Chu, C. M. ; Yao, C. F. / Novel synthesis of alkenes via triethylborane-induced free-radical reactions of alkyl iodides and β-nitrostyrenes. In: Journal of Organic Chemistry. 2001 ; Vol. 66, No. 18. pp. 6021-6028.
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abstract = "Reactions of (E)-β-nitrostyrenes 1 and triethylborane 2 or tricyclohexylborane 4 in THF solution at room temperature in the presence of oxygen in the air as radical initiator generate high yields of trans-alkenes (E)-3 or (E)-5. Medium to high yields of different (E)-alkenes (E)-5, 7, 10, 12, and 14 also can be prepared when 1 reacts with different radicals, prepared from secondary alkyl iodides 6 and 8 or tertiary alkyl iodides 9, 11, and 13, in the presence of 2 and air as radical initiator. The generation of the only product (E)-alkenes can be explained by the generation of the benzylic radical A and/or B as the intermediate only and the mechanism is similar to Scheme 1. Both (E)- and (Z)-16a-c are generated when (E)- and (Z)-15a-c are used to react with adamantyl radical under similar conditions. Only (Z)-16d was observed when either (E)- or (Z)-15d was used to react with adamantyl radical. The generation of the (E)- and/or (Z)-alkenes can be explained by the free rotation of the A and/or B to generate A′ and/or B′ and vice versa, and the mechanism is proposed to be a free-radical reaction via NO2/alkyl substitution and is shown as Scheme 2.",
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AU - Chu, C. M.

AU - Yao, C. F.

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N2 - Reactions of (E)-β-nitrostyrenes 1 and triethylborane 2 or tricyclohexylborane 4 in THF solution at room temperature in the presence of oxygen in the air as radical initiator generate high yields of trans-alkenes (E)-3 or (E)-5. Medium to high yields of different (E)-alkenes (E)-5, 7, 10, 12, and 14 also can be prepared when 1 reacts with different radicals, prepared from secondary alkyl iodides 6 and 8 or tertiary alkyl iodides 9, 11, and 13, in the presence of 2 and air as radical initiator. The generation of the only product (E)-alkenes can be explained by the generation of the benzylic radical A and/or B as the intermediate only and the mechanism is similar to Scheme 1. Both (E)- and (Z)-16a-c are generated when (E)- and (Z)-15a-c are used to react with adamantyl radical under similar conditions. Only (Z)-16d was observed when either (E)- or (Z)-15d was used to react with adamantyl radical. The generation of the (E)- and/or (Z)-alkenes can be explained by the free rotation of the A and/or B to generate A′ and/or B′ and vice versa, and the mechanism is proposed to be a free-radical reaction via NO2/alkyl substitution and is shown as Scheme 2.

AB - Reactions of (E)-β-nitrostyrenes 1 and triethylborane 2 or tricyclohexylborane 4 in THF solution at room temperature in the presence of oxygen in the air as radical initiator generate high yields of trans-alkenes (E)-3 or (E)-5. Medium to high yields of different (E)-alkenes (E)-5, 7, 10, 12, and 14 also can be prepared when 1 reacts with different radicals, prepared from secondary alkyl iodides 6 and 8 or tertiary alkyl iodides 9, 11, and 13, in the presence of 2 and air as radical initiator. The generation of the only product (E)-alkenes can be explained by the generation of the benzylic radical A and/or B as the intermediate only and the mechanism is similar to Scheme 1. Both (E)- and (Z)-16a-c are generated when (E)- and (Z)-15a-c are used to react with adamantyl radical under similar conditions. Only (Z)-16d was observed when either (E)- or (Z)-15d was used to react with adamantyl radical. The generation of the (E)- and/or (Z)-alkenes can be explained by the free rotation of the A and/or B to generate A′ and/or B′ and vice versa, and the mechanism is proposed to be a free-radical reaction via NO2/alkyl substitution and is shown as Scheme 2.

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