Room-temperature metallation of 2-substituted 1,3-dithiane derivatives and subsequent coupling with 2,3-disubstituted oxiranes

Mitsuaki Ide, Masaya Nakata

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Abstract

2-Substituted 1,3-dithiane derivatives, (S)-1(t-butyldiphenylsiloxy)-2- (1,3-dithian-2-yl)propane (9), (S)-1-(t-butyldimethylsiloxy)-2-(1,3-dithian- 2-yl)propane, 1-(t-butyldiphenylsiloxy)-2-(1,3-dithian-2-yl)-2-methylpropane, and 1,2-bis-(t-butyldiphenylsiloxy)-3-(1,3-dithian-2-yl)propane, were subjected to lithiation in THF with n-BuLi at room temperature (r.t.); the resulting anions reacted with 2,3-disubstituted oxirane, trans-2-methyl-3- (triphenylmethoxymethyl)oxirane(22), at r.t., giving the coupling products in satisfactory yield. On the other hand, the lithium salt formed in ether from (S)2-(1,3-dithian-2-yl)-1-(4-methoxybenzyloxy)propane with n-BuLi at r.t. reacted with 22 at r.t. in the presence of hexamethylphosphoric triamide to afford the coupling product in moderate yield. In addition, a mixed organometallic reagent, n-BuLi/Bu2Mg, was found to be an effective metallation reagent for 9 and the resulting anion reacted with 22 to afford the coupling product in good yield.

Original languageEnglish
Pages (from-to)2491-2499
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume72
Issue number11
Publication statusPublished - 1999 Nov

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Propane
Epoxy Compounds
Derivatives
Ethylene Oxide
Anions
Hempa
Temperature
Organometallics
Lithium
Ether
Salts
1,3-dithiane
n-butyllithium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Room-temperature metallation of 2-substituted 1,3-dithiane derivatives and subsequent coupling with 2,3-disubstituted oxiranes. / Ide, Mitsuaki; Nakata, Masaya.

In: Bulletin of the Chemical Society of Japan, Vol. 72, No. 11, 11.1999, p. 2491-2499.

Research output: Contribution to journalArticle

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abstract = "2-Substituted 1,3-dithiane derivatives, (S)-1(t-butyldiphenylsiloxy)-2- (1,3-dithian-2-yl)propane (9), (S)-1-(t-butyldimethylsiloxy)-2-(1,3-dithian- 2-yl)propane, 1-(t-butyldiphenylsiloxy)-2-(1,3-dithian-2-yl)-2-methylpropane, and 1,2-bis-(t-butyldiphenylsiloxy)-3-(1,3-dithian-2-yl)propane, were subjected to lithiation in THF with n-BuLi at room temperature (r.t.); the resulting anions reacted with 2,3-disubstituted oxirane, trans-2-methyl-3- (triphenylmethoxymethyl)oxirane(22), at r.t., giving the coupling products in satisfactory yield. On the other hand, the lithium salt formed in ether from (S)2-(1,3-dithian-2-yl)-1-(4-methoxybenzyloxy)propane with n-BuLi at r.t. reacted with 22 at r.t. in the presence of hexamethylphosphoric triamide to afford the coupling product in moderate yield. In addition, a mixed organometallic reagent, n-BuLi/Bu2Mg, was found to be an effective metallation reagent for 9 and the resulting anion reacted with 22 to afford the coupling product in good yield.",
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N2 - 2-Substituted 1,3-dithiane derivatives, (S)-1(t-butyldiphenylsiloxy)-2- (1,3-dithian-2-yl)propane (9), (S)-1-(t-butyldimethylsiloxy)-2-(1,3-dithian- 2-yl)propane, 1-(t-butyldiphenylsiloxy)-2-(1,3-dithian-2-yl)-2-methylpropane, and 1,2-bis-(t-butyldiphenylsiloxy)-3-(1,3-dithian-2-yl)propane, were subjected to lithiation in THF with n-BuLi at room temperature (r.t.); the resulting anions reacted with 2,3-disubstituted oxirane, trans-2-methyl-3- (triphenylmethoxymethyl)oxirane(22), at r.t., giving the coupling products in satisfactory yield. On the other hand, the lithium salt formed in ether from (S)2-(1,3-dithian-2-yl)-1-(4-methoxybenzyloxy)propane with n-BuLi at r.t. reacted with 22 at r.t. in the presence of hexamethylphosphoric triamide to afford the coupling product in moderate yield. In addition, a mixed organometallic reagent, n-BuLi/Bu2Mg, was found to be an effective metallation reagent for 9 and the resulting anion reacted with 22 to afford the coupling product in good yield.

AB - 2-Substituted 1,3-dithiane derivatives, (S)-1(t-butyldiphenylsiloxy)-2- (1,3-dithian-2-yl)propane (9), (S)-1-(t-butyldimethylsiloxy)-2-(1,3-dithian- 2-yl)propane, 1-(t-butyldiphenylsiloxy)-2-(1,3-dithian-2-yl)-2-methylpropane, and 1,2-bis-(t-butyldiphenylsiloxy)-3-(1,3-dithian-2-yl)propane, were subjected to lithiation in THF with n-BuLi at room temperature (r.t.); the resulting anions reacted with 2,3-disubstituted oxirane, trans-2-methyl-3- (triphenylmethoxymethyl)oxirane(22), at r.t., giving the coupling products in satisfactory yield. On the other hand, the lithium salt formed in ether from (S)2-(1,3-dithian-2-yl)-1-(4-methoxybenzyloxy)propane with n-BuLi at r.t. reacted with 22 at r.t. in the presence of hexamethylphosphoric triamide to afford the coupling product in moderate yield. In addition, a mixed organometallic reagent, n-BuLi/Bu2Mg, was found to be an effective metallation reagent for 9 and the resulting anion reacted with 22 to afford the coupling product in good yield.

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