Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions

M. Nakata, T. Ishiyama, S. Akamatsu, Y. Hirose, H. Maruoka, R. Suzuki, K. Tatsuta

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The oligomycin B spiroketal portion, [2S,2(2R),3S,6R,8S,8(3R),9S,10R,11S]-2-[2-(t-butyldiphenylsilyloxy)pro pyl]-8-[3-(hydroxymethyl)pentyl]-3,9,11-trimethyl-1,7-dioxaspiro[5,5]u ndecane-5,10-diol (2), and polypropionate portion, ethyl (2E,4S,5R,6R,7S,8S,9R,10S,12R,13S,14R,16E)-5-(t-butyldimethylsilyloxy) -7,9-(isopropylidenedioxy)-12,13-(4-methoxybenzylidenedioxy)4,6,8,10,1 2,14-hexamethyl-11-oxo-18-phenylsulfonyloctadeca-2,16-dienoate (3), have been synthesized. The C19-C21 Wittig salt, [(2S,3R)-2-ethyl-3,4-isopropylidenedioxy)butyl]triphenylphosphonium iodide (6), prepared from 2-butene-1,4-diol via Sharpless epoxidation, was coupled with the C22-C27 aldehyde, benzyl 2,4-dideoxy-3-O-(4-methoxybenzyl)-2,4-di-C-methyl-α,β-L-galacto-hexo dialdopyranoside-(1,5) (7), prepared from (Z)-2-butene-1,4-diol via Sharpless epoxidation and the Brown's crotylboration. The resulting coupling product was transformed to the C19-C27 lactone, [3S,4R,5R,6S,6(3R,4R)]-6-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-4-( 4-methoxybenzyloxy)-3,5-dimethyl-3,4,5,6-tetrahydro-2H-pyran-2-one (4). The C28-C34 organostannane compound, (2R,4S,5S,7RS)-2-(t-butyldiphenylsilyloxy)-5-methyl-7-(tributylstannyl )-4-(triethylsilyloxy)-7-[(2-trimethylsilylethoxy)methoxy]heptane (5b), was prepared from (R)-methyl 3-hydroxybutyrate via the Brown's crotylboration and the Still's stannylation. After lithiation of 5b with butyllithium, the resulting α-alkoxy organolithium compound was coupled with 4 and the product was converted to the C19-C34 spiroketal, [2S,2(2R),3S,6R,8S,8(3R,4R),9S,10R,11S]-2-[2-t-butyldiphenylsilyloxy)p ropyl]-8-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-10-(4-methoxybenzyl oxy)-3,9,11-trimethyl-1,7-dioxaspiro[5,5]undecan-5-ol (37). The synthetic 2, derived fron 37, was identical to the oligomycins (A, B, C mixture) degradation product in all respects, which elucidates the absolute stereochemistry of oligomycin B (1b). The C3-C9 aldehyde, (2-trimethylsilylethoxy)methyl 2,4,5-trideoxy-3-O-(4-methoxybenzyl)-2,4,6-tri-C-methyl-D-glycero-α-L -ido-heptodialdopyranoside-(1,5) (9), was prepared from (2S)-3-(t-butyldimethylsilyloxy)-2-methylpropanal via Keck's crotylstannane addition and Brown's crotylboration. The aldol coupling between the zinc enolate of the C10-C16 ketone, t-butyldimethylsilyl 2,3,7,8-tetradeoxy-4-O-(4-methoxybenzyl)-3,5-di-C-methyl-α-L-xylo-oct opyranosid-6-ulose (10), prepared from methyl (R)-(+)-lactate via Brown's crotylboration and a metallated methoxyallene addition, and aldehyde 9 gave the C8-C9 syn, C9-C10 syn product, which was transformed to the oligomycin B polypropionate portion 3 through elongation of the C1-C2 and C17-C18 carbon units.

Original languageEnglish
Pages (from-to)967-989
Number of pages23
JournalBulletin of the Chemical Society of Japan
Volume68
Issue number3
Publication statusPublished - 1995 Mar

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Oligomycins
Aldehydes
Epoxidation
Pyrans
Heptanes
Stereochemistry
3-Hydroxybutyric Acid
Iodides
Lactones
Ketones
Zinc
Elongation
Lactic Acid
Carbon
Salts
Degradation
spiroketal
oligomycin B
penitricin C

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Nakata, M., Ishiyama, T., Akamatsu, S., Hirose, Y., Maruoka, H., Suzuki, R., & Tatsuta, K. (1995). Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions. Bulletin of the Chemical Society of Japan, 68(3), 967-989.

Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions. / Nakata, M.; Ishiyama, T.; Akamatsu, S.; Hirose, Y.; Maruoka, H.; Suzuki, R.; Tatsuta, K.

In: Bulletin of the Chemical Society of Japan, Vol. 68, No. 3, 03.1995, p. 967-989.

Research output: Contribution to journalArticle

Nakata, M, Ishiyama, T, Akamatsu, S, Hirose, Y, Maruoka, H, Suzuki, R & Tatsuta, K 1995, 'Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions', Bulletin of the Chemical Society of Japan, vol. 68, no. 3, pp. 967-989.
Nakata M, Ishiyama T, Akamatsu S, Hirose Y, Maruoka H, Suzuki R et al. Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions. Bulletin of the Chemical Society of Japan. 1995 Mar;68(3):967-989.
Nakata, M. ; Ishiyama, T. ; Akamatsu, S. ; Hirose, Y. ; Maruoka, H. ; Suzuki, R. ; Tatsuta, K. / Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions. In: Bulletin of the Chemical Society of Japan. 1995 ; Vol. 68, No. 3. pp. 967-989.
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abstract = "The oligomycin B spiroketal portion, [2S,2(2R),3S,6R,8S,8(3R),9S,10R,11S]-2-[2-(t-butyldiphenylsilyloxy)pro pyl]-8-[3-(hydroxymethyl)pentyl]-3,9,11-trimethyl-1,7-dioxaspiro[5,5]u ndecane-5,10-diol (2), and polypropionate portion, ethyl (2E,4S,5R,6R,7S,8S,9R,10S,12R,13S,14R,16E)-5-(t-butyldimethylsilyloxy) -7,9-(isopropylidenedioxy)-12,13-(4-methoxybenzylidenedioxy)4,6,8,10,1 2,14-hexamethyl-11-oxo-18-phenylsulfonyloctadeca-2,16-dienoate (3), have been synthesized. The C19-C21 Wittig salt, [(2S,3R)-2-ethyl-3,4-isopropylidenedioxy)butyl]triphenylphosphonium iodide (6), prepared from 2-butene-1,4-diol via Sharpless epoxidation, was coupled with the C22-C27 aldehyde, benzyl 2,4-dideoxy-3-O-(4-methoxybenzyl)-2,4-di-C-methyl-α,β-L-galacto-hexo dialdopyranoside-(1,5) (7), prepared from (Z)-2-butene-1,4-diol via Sharpless epoxidation and the Brown's crotylboration. The resulting coupling product was transformed to the C19-C27 lactone, [3S,4R,5R,6S,6(3R,4R)]-6-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-4-( 4-methoxybenzyloxy)-3,5-dimethyl-3,4,5,6-tetrahydro-2H-pyran-2-one (4). The C28-C34 organostannane compound, (2R,4S,5S,7RS)-2-(t-butyldiphenylsilyloxy)-5-methyl-7-(tributylstannyl )-4-(triethylsilyloxy)-7-[(2-trimethylsilylethoxy)methoxy]heptane (5b), was prepared from (R)-methyl 3-hydroxybutyrate via the Brown's crotylboration and the Still's stannylation. After lithiation of 5b with butyllithium, the resulting α-alkoxy organolithium compound was coupled with 4 and the product was converted to the C19-C34 spiroketal, [2S,2(2R),3S,6R,8S,8(3R,4R),9S,10R,11S]-2-[2-t-butyldiphenylsilyloxy)p ropyl]-8-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-10-(4-methoxybenzyl oxy)-3,9,11-trimethyl-1,7-dioxaspiro[5,5]undecan-5-ol (37). The synthetic 2, derived fron 37, was identical to the oligomycins (A, B, C mixture) degradation product in all respects, which elucidates the absolute stereochemistry of oligomycin B (1b). The C3-C9 aldehyde, (2-trimethylsilylethoxy)methyl 2,4,5-trideoxy-3-O-(4-methoxybenzyl)-2,4,6-tri-C-methyl-D-glycero-α-L -ido-heptodialdopyranoside-(1,5) (9), was prepared from (2S)-3-(t-butyldimethylsilyloxy)-2-methylpropanal via Keck's crotylstannane addition and Brown's crotylboration. The aldol coupling between the zinc enolate of the C10-C16 ketone, t-butyldimethylsilyl 2,3,7,8-tetradeoxy-4-O-(4-methoxybenzyl)-3,5-di-C-methyl-α-L-xylo-oct opyranosid-6-ulose (10), prepared from methyl (R)-(+)-lactate via Brown's crotylboration and a metallated methoxyallene addition, and aldehyde 9 gave the C8-C9 syn, C9-C10 syn product, which was transformed to the oligomycin B polypropionate portion 3 through elongation of the C1-C2 and C17-C18 carbon units.",
author = "M. Nakata and T. Ishiyama and S. Akamatsu and Y. Hirose and H. Maruoka and R. Suzuki and K. Tatsuta",
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TY - JOUR

T1 - Synthetic studies on oligomycins. Synthesis of the oligomycin B spiroketal and polypropionate portions

AU - Nakata, M.

AU - Ishiyama, T.

AU - Akamatsu, S.

AU - Hirose, Y.

AU - Maruoka, H.

AU - Suzuki, R.

AU - Tatsuta, K.

PY - 1995/3

Y1 - 1995/3

N2 - The oligomycin B spiroketal portion, [2S,2(2R),3S,6R,8S,8(3R),9S,10R,11S]-2-[2-(t-butyldiphenylsilyloxy)pro pyl]-8-[3-(hydroxymethyl)pentyl]-3,9,11-trimethyl-1,7-dioxaspiro[5,5]u ndecane-5,10-diol (2), and polypropionate portion, ethyl (2E,4S,5R,6R,7S,8S,9R,10S,12R,13S,14R,16E)-5-(t-butyldimethylsilyloxy) -7,9-(isopropylidenedioxy)-12,13-(4-methoxybenzylidenedioxy)4,6,8,10,1 2,14-hexamethyl-11-oxo-18-phenylsulfonyloctadeca-2,16-dienoate (3), have been synthesized. The C19-C21 Wittig salt, [(2S,3R)-2-ethyl-3,4-isopropylidenedioxy)butyl]triphenylphosphonium iodide (6), prepared from 2-butene-1,4-diol via Sharpless epoxidation, was coupled with the C22-C27 aldehyde, benzyl 2,4-dideoxy-3-O-(4-methoxybenzyl)-2,4-di-C-methyl-α,β-L-galacto-hexo dialdopyranoside-(1,5) (7), prepared from (Z)-2-butene-1,4-diol via Sharpless epoxidation and the Brown's crotylboration. The resulting coupling product was transformed to the C19-C27 lactone, [3S,4R,5R,6S,6(3R,4R)]-6-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-4-( 4-methoxybenzyloxy)-3,5-dimethyl-3,4,5,6-tetrahydro-2H-pyran-2-one (4). The C28-C34 organostannane compound, (2R,4S,5S,7RS)-2-(t-butyldiphenylsilyloxy)-5-methyl-7-(tributylstannyl )-4-(triethylsilyloxy)-7-[(2-trimethylsilylethoxy)methoxy]heptane (5b), was prepared from (R)-methyl 3-hydroxybutyrate via the Brown's crotylboration and the Still's stannylation. After lithiation of 5b with butyllithium, the resulting α-alkoxy organolithium compound was coupled with 4 and the product was converted to the C19-C34 spiroketal, [2S,2(2R),3S,6R,8S,8(3R,4R),9S,10R,11S]-2-[2-t-butyldiphenylsilyloxy)p ropyl]-8-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-10-(4-methoxybenzyl oxy)-3,9,11-trimethyl-1,7-dioxaspiro[5,5]undecan-5-ol (37). The synthetic 2, derived fron 37, was identical to the oligomycins (A, B, C mixture) degradation product in all respects, which elucidates the absolute stereochemistry of oligomycin B (1b). The C3-C9 aldehyde, (2-trimethylsilylethoxy)methyl 2,4,5-trideoxy-3-O-(4-methoxybenzyl)-2,4,6-tri-C-methyl-D-glycero-α-L -ido-heptodialdopyranoside-(1,5) (9), was prepared from (2S)-3-(t-butyldimethylsilyloxy)-2-methylpropanal via Keck's crotylstannane addition and Brown's crotylboration. The aldol coupling between the zinc enolate of the C10-C16 ketone, t-butyldimethylsilyl 2,3,7,8-tetradeoxy-4-O-(4-methoxybenzyl)-3,5-di-C-methyl-α-L-xylo-oct opyranosid-6-ulose (10), prepared from methyl (R)-(+)-lactate via Brown's crotylboration and a metallated methoxyallene addition, and aldehyde 9 gave the C8-C9 syn, C9-C10 syn product, which was transformed to the oligomycin B polypropionate portion 3 through elongation of the C1-C2 and C17-C18 carbon units.

AB - The oligomycin B spiroketal portion, [2S,2(2R),3S,6R,8S,8(3R),9S,10R,11S]-2-[2-(t-butyldiphenylsilyloxy)pro pyl]-8-[3-(hydroxymethyl)pentyl]-3,9,11-trimethyl-1,7-dioxaspiro[5,5]u ndecane-5,10-diol (2), and polypropionate portion, ethyl (2E,4S,5R,6R,7S,8S,9R,10S,12R,13S,14R,16E)-5-(t-butyldimethylsilyloxy) -7,9-(isopropylidenedioxy)-12,13-(4-methoxybenzylidenedioxy)4,6,8,10,1 2,14-hexamethyl-11-oxo-18-phenylsulfonyloctadeca-2,16-dienoate (3), have been synthesized. The C19-C21 Wittig salt, [(2S,3R)-2-ethyl-3,4-isopropylidenedioxy)butyl]triphenylphosphonium iodide (6), prepared from 2-butene-1,4-diol via Sharpless epoxidation, was coupled with the C22-C27 aldehyde, benzyl 2,4-dideoxy-3-O-(4-methoxybenzyl)-2,4-di-C-methyl-α,β-L-galacto-hexo dialdopyranoside-(1,5) (7), prepared from (Z)-2-butene-1,4-diol via Sharpless epoxidation and the Brown's crotylboration. The resulting coupling product was transformed to the C19-C27 lactone, [3S,4R,5R,6S,6(3R,4R)]-6-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-4-( 4-methoxybenzyloxy)-3,5-dimethyl-3,4,5,6-tetrahydro-2H-pyran-2-one (4). The C28-C34 organostannane compound, (2R,4S,5S,7RS)-2-(t-butyldiphenylsilyloxy)-5-methyl-7-(tributylstannyl )-4-(triethylsilyloxy)-7-[(2-trimethylsilylethoxy)methoxy]heptane (5b), was prepared from (R)-methyl 3-hydroxybutyrate via the Brown's crotylboration and the Still's stannylation. After lithiation of 5b with butyllithium, the resulting α-alkoxy organolithium compound was coupled with 4 and the product was converted to the C19-C34 spiroketal, [2S,2(2R),3S,6R,8S,8(3R,4R),9S,10R,11S]-2-[2-t-butyldiphenylsilyloxy)p ropyl]-8-[3-ethyl-4,5-(isopropylidenedioxy)pentyl]-10-(4-methoxybenzyl oxy)-3,9,11-trimethyl-1,7-dioxaspiro[5,5]undecan-5-ol (37). The synthetic 2, derived fron 37, was identical to the oligomycins (A, B, C mixture) degradation product in all respects, which elucidates the absolute stereochemistry of oligomycin B (1b). The C3-C9 aldehyde, (2-trimethylsilylethoxy)methyl 2,4,5-trideoxy-3-O-(4-methoxybenzyl)-2,4,6-tri-C-methyl-D-glycero-α-L -ido-heptodialdopyranoside-(1,5) (9), was prepared from (2S)-3-(t-butyldimethylsilyloxy)-2-methylpropanal via Keck's crotylstannane addition and Brown's crotylboration. The aldol coupling between the zinc enolate of the C10-C16 ketone, t-butyldimethylsilyl 2,3,7,8-tetradeoxy-4-O-(4-methoxybenzyl)-3,5-di-C-methyl-α-L-xylo-oct opyranosid-6-ulose (10), prepared from methyl (R)-(+)-lactate via Brown's crotylboration and a metallated methoxyallene addition, and aldehyde 9 gave the C8-C9 syn, C9-C10 syn product, which was transformed to the oligomycin B polypropionate portion 3 through elongation of the C1-C2 and C17-C18 carbon units.

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