Highly diastereo- and enantioselective aziridination of α,β-unsaturated amides with diaziridine and mechanistic consideration on its stereochemistry

Hiroyuki Ishihara, Kiyoto Hori, Hiroyasu Sugihara, Yoshio Ito, Tsutomu Katsuki

研究成果: ジャーナルへの寄稿記事

26 引用 (Scopus)

抄録

During studies of aziridination of α,β-unsaturated amides with diaziridine, we found that we could prepare both the cis- and trans-aziridinecarboxamides by choosing an appropriately substituted diaziridine. While 3-monosubstituted diaziridine 2 was suitable for the trans-selective aziridination, employment of 3,3-dialkyldiaziridine 1 resulted in the formation of cis-aziridine carboxamides, irrespective of the geometry of the substrate (Scheme 1 and Tables 1 and 2). To elucidate the unique nonstereospecificity and to expand these aziridinations to asymmetric ones, several optically active diaziridines were newly prepared. Aziridination with an optically active 3-monosubstituted diaziridine, 3-cyclohexyl-1-[(1R)-1-phenylethyl]diaziridine 16, proceeded smoothly with high trans-selectivity as well as excellent enantioselectivity (up to 98% ee; see Table 3). On the other hand, highly enantioselective cis-aziridination was achieved (> 99% ee) with optically active 3.3-dimethyl-1-[(1R)-1-phenylethyl]diaziridine 15, though the yield was low (4%). This aziridination was considered to proceed stepwise by way of the enolate intermediate (Scheme 2). Careful inspection of the stereochemistry and its solvent-dependence suggested that the diastereoselection of the reaction was kinetically controlled: the 1,4-addition of N-lithiated diaziridine was a crucial step for determination of the stereochemical course of the aziridination (Figs. 2-4).

元の言語英語
ページ(範囲)4272-4286
ページ数15
ジャーナルHelvetica Chimica Acta
85
発行部数12
DOI
出版物ステータス出版済み - 12 1 2002

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Stereochemistry
Enantioselectivity
stereochemistry
Amides
amides
Inspection
Geometry
Substrates
inspection
selectivity
geometry
aziridine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Biochemistry
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Highly diastereo- and enantioselective aziridination of α,β-unsaturated amides with diaziridine and mechanistic consideration on its stereochemistry. / Ishihara, Hiroyuki; Hori, Kiyoto; Sugihara, Hiroyasu; Ito, Yoshio; Katsuki, Tsutomu.

:: Helvetica Chimica Acta, 巻 85, 番号 12, 01.12.2002, p. 4272-4286.

研究成果: ジャーナルへの寄稿記事

Ishihara, Hiroyuki ; Hori, Kiyoto ; Sugihara, Hiroyasu ; Ito, Yoshio ; Katsuki, Tsutomu. / Highly diastereo- and enantioselective aziridination of α,β-unsaturated amides with diaziridine and mechanistic consideration on its stereochemistry. :: Helvetica Chimica Acta. 2002 ; 巻 85, 番号 12. pp. 4272-4286.
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abstract = "During studies of aziridination of α,β-unsaturated amides with diaziridine, we found that we could prepare both the cis- and trans-aziridinecarboxamides by choosing an appropriately substituted diaziridine. While 3-monosubstituted diaziridine 2 was suitable for the trans-selective aziridination, employment of 3,3-dialkyldiaziridine 1 resulted in the formation of cis-aziridine carboxamides, irrespective of the geometry of the substrate (Scheme 1 and Tables 1 and 2). To elucidate the unique nonstereospecificity and to expand these aziridinations to asymmetric ones, several optically active diaziridines were newly prepared. Aziridination with an optically active 3-monosubstituted diaziridine, 3-cyclohexyl-1-[(1R)-1-phenylethyl]diaziridine 16, proceeded smoothly with high trans-selectivity as well as excellent enantioselectivity (up to 98{\%} ee; see Table 3). On the other hand, highly enantioselective cis-aziridination was achieved (> 99{\%} ee) with optically active 3.3-dimethyl-1-[(1R)-1-phenylethyl]diaziridine 15, though the yield was low (4{\%}). This aziridination was considered to proceed stepwise by way of the enolate intermediate (Scheme 2). Careful inspection of the stereochemistry and its solvent-dependence suggested that the diastereoselection of the reaction was kinetically controlled: the 1,4-addition of N-lithiated diaziridine was a crucial step for determination of the stereochemical course of the aziridination (Figs. 2-4).",
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T1 - Highly diastereo- and enantioselective aziridination of α,β-unsaturated amides with diaziridine and mechanistic consideration on its stereochemistry

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AU - Hori, Kiyoto

AU - Sugihara, Hiroyasu

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AU - Katsuki, Tsutomu

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AB - During studies of aziridination of α,β-unsaturated amides with diaziridine, we found that we could prepare both the cis- and trans-aziridinecarboxamides by choosing an appropriately substituted diaziridine. While 3-monosubstituted diaziridine 2 was suitable for the trans-selective aziridination, employment of 3,3-dialkyldiaziridine 1 resulted in the formation of cis-aziridine carboxamides, irrespective of the geometry of the substrate (Scheme 1 and Tables 1 and 2). To elucidate the unique nonstereospecificity and to expand these aziridinations to asymmetric ones, several optically active diaziridines were newly prepared. Aziridination with an optically active 3-monosubstituted diaziridine, 3-cyclohexyl-1-[(1R)-1-phenylethyl]diaziridine 16, proceeded smoothly with high trans-selectivity as well as excellent enantioselectivity (up to 98% ee; see Table 3). On the other hand, highly enantioselective cis-aziridination was achieved (> 99% ee) with optically active 3.3-dimethyl-1-[(1R)-1-phenylethyl]diaziridine 15, though the yield was low (4%). This aziridination was considered to proceed stepwise by way of the enolate intermediate (Scheme 2). Careful inspection of the stereochemistry and its solvent-dependence suggested that the diastereoselection of the reaction was kinetically controlled: the 1,4-addition of N-lithiated diaziridine was a crucial step for determination of the stereochemical course of the aziridination (Figs. 2-4).

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