二環性糖供与体による立体選択的グリコシル化反応の開発と糖脂質合成への応用

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Title

二環性糖供与体による立体選択的グリコシル化反応の開発

_{と糖脂質合成への応用( 本文(Fulltext) )}

Author(s)

八神, 奈帆子

Report No.(Doctoral

Degree)

博士(農学) 甲第688号

Issue Date

2018-03-13

Type

博士論文

Version

ETD

URL

http://hdl.handle.net/20.500.12099/75246

※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。

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஧⎔ᛶ⢾౪୚య࡟ࡼࡿ❧య㑅ᢥⓗࢢࣜࢥࢩࣝ໬཯ᛂࡢ㛤Ⓨ

࡜⢾⬡㉁ྜᡂ࡬ࡢᛂ⏝

2017 ᖺ

ᒱ㜧኱Ꮫ኱Ꮫ㝔㐃ྜ㎰Ꮫ◊✲⛉

⏕≀㈨※⛉Ꮫ

(ᒱ㜧኱Ꮫ)

ඵ⚄ ዉᕹᏊ

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஧⎔ᛶ⢾౪୚య࡟ࡼࡿ❧య㑅ᢥⓗࢢࣜࢥࢩࣝ໬཯ᛂࡢ㛤Ⓨ

࡜⢾⬡㉁ྜᡂ࡬ࡢᛂ⏝

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-1- ␎ㄒ⾲ 03 ⥴ゝ 05 ➨୍㒊 2,3-⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓ 1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࢻ໬ࡢ᳨ウ ➨୍❶ ⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍⠇ ⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓ❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬཯ᛂ࡟㛵ࡍࡿ◊✲౛ 08 ➨஧⠇ ⎔≧ࢩࣜࣝ⣔ಖㆤᇶࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ 11 ➨஧❶ ஧⎔ᛶ⢾౪୚యࡢྜᡂ 12 ➨୕❶ ஧⎔ᛶ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ 14 ➨ᅄ❶ ඵဨ⎔⎔≧ಖㆤࡋࡓ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍⠇ 2,3-o-Xylylene ᆺ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍㡯 4,6 ఩Ỉ㓟ᇶಖㆤᇶ࡟ࡼࡿᙳ㡪ࡢ᳨ド 16 ➨஧㡯 ⁐፹࡟ࡼࡿᙳ㡪ࡢ᳨ド 18 ➨୕㡯 ࣝ࢖ࢫ㓟ཬࡧ⬺㞳ᇶ࡟ࡼࡿᙳ㡪ࡢ᳨ド 19 ➨ᅄ㡯 ཷᐜయ࡟ࡼࡿᙳ㡪ࡢ᳨ド 23 ➨஬㡯 ␗ᛶ໬཯ᛂ࡟㛵ࡍࡿ᳨ド 26 ➨஧⠇ 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍㡯 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ⢾౪୚యࡢྜᡂ࡜ࢢࣜࢥࢩࢻ໬཯ᛂ 29 ➨஧㡯 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᇶ㝖ཤࡢ᳨ウ 31 ➨஬❶ NMR ཬࡧᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸ࡓ⎔≧⢾౪୚యࡢᵓ㐀ゎᯒ ➨୍⠇ NMR ࢆ⏝࠸ࡓ⎔≧ಖㆤ⢾౪୚యࡢ㓄ᗙゎᯒ 35 ➨஧⠇ ᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸ࡓ⎔≧ಖㆤ⢾౪୚యࡢ㓄ᗙゎᯒ 42 ➨භ❶ 1,2-trans-㑅ᢥᛶⓎ⌧ᶵᵓ࡟㛵ࡍࡿ⪃ᐹ 44 ⥲ᣓ 46 ᐇ㦂ࡢ㒊 47

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-2- ➨஧㒊 ஧⎔ᛶ⢾౪୚యࢆ⏝࠸ࡓE-ࢢࣜࢭࣟ⢾⬡㉁ྜᡂ ➨୍❶ ࢢࣜࢭࣟ⢾⬡㉁࡟㛵ࡍࡿ◊✲౛ 108 ➨஧❶ ྜᡂᡓ␎ 113 ➨୕❶ 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ⢾౪୚యࡢྜᡂ 115 ➨ᅄ❶ ඹ㏻ࢢࣝࢥࢩࣝࢢࣜࢭ࣮ࣟࣝࣘࢽࢵࢺࡢྜᡂ ➨୍⠇ ࢖ࢯࣉࣟࣆࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ 116 ➨஧⠇ ࢪ࢔ࢩࣝᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ ➨୍㡯 ࢪ࢔ࢩࣝᆺࢢࣜࢭ࣮ࣟࣝࡢྜᡂ 117 ➨஧㡯 ࢪ࢔ࢩࣝᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ 118 ➨୕⠇ ࣔࣀ࢔ࢩࣝᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ ➨୍㡯 ࣔࣀ࢔ࢩࣝᆺࢢࣜࢭ࣮ࣟࣝࡢྜᡂ࡜ࢢࣜࢥࢩࣝ໬཯ᛂ 119 ➨஧㡯 2,6-ࢪ࣓ࢳࣝ-4-࣊࢟ࢩࣟ࢟ࢩ࣋ࣥࢰ࢖ࣝᆺࢢࣜࢭ࣮ࣟࣝࡢྜᡂ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ ₁₂₁ ➨ᅄ⠇ ࢽࢺࣟ࣋ࣥࢪࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ ➨୍㡯 p-ࢽࢺࣟ࣋ࣥࢪࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝࡢྜᡂ 127 ➨஧㡯 p-ࢽࢺࣟ࣋ࣥࢪࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ 128 ➨୕㡯 o-ࢽࢺࣟ࣋ࣥࢪࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝࡢྜᡂ 130 ➨ᅄ㡯 o-ࢽࢺࣟ࣋ࣥࢪࣜࢹࣥᆺࢢࣜࢭ࣮ࣟࣝ࡜ࡢࢢࣜࢥࢩࣝ໬཯ᛂ 131 ➨஬❶ ࢪࢢࣝࢥࢩࣝࢪ࢔ࢩࣝࢢࣜࢭ࣮ࣟࣝ㦵᱁ࡢྜᡂ ➨୍⠇ ࢢࣝࢥࢩࣝࢪ࢔ࢩࣝࢢࣜࢭ࣮ࣟࣝࢆ⤒⏤ࡋࡓྜᡂ 133 ➨஧⠇ ࢪࢢࣝࢥࢩࣝࢢࣜࢭ࣮ࣟࣝࢆ⤒⏤ࡋࡓྜᡂ 136 ➨භ❶ ࢪࢢࣝࢥࢩࣝࢪ࢔ࢩࣝࢢࣜࢭ࣮ࣟࣝࡢྜᡂ 139 ⥲ᣓ 141 ᐇ㦂ࡢ㒊 142 ㅰ㎡ 176

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-3- ␎ㄒ⾲

ᮏㄽᩥ࡟࠾࠸࡚ࠊ௨ୗ࡟♧ࡋࡓ␎ㄒࢆ⏝࠸ࡓࠋ

Ac : acetyl

ADA : anisaldehyde dimethyl acetal

BDA : 2’,3’-dimethoxybutane-2’,3’-diyl

Bn : benzyl

Bu : butyl

Bz : benzoyl

CPME : cyclopentyl methyl ether CSA : (s) camphor-10-sulfonic acid

DBU : 1,8-diazabicyclo[5.4.0]undec-7-ene DCC : N,N'-dicyclohexylcarbodiimide

DDQ : 2,3-dichloro-5,6-dicyano-p-benzoquinone DIAD : diisopropyl azodicarboxylate

DMAP : N,N-dimethyl-4-aminopyridine DMF : N,N-dimethylformamide DMSO : dimethyl sulfoxide

DMTSF : dimethyl(methylthio)sulfonium tetrafluoroborate

DMTST : dimethyl(methylthio)sulfonium trifluoromethanesulfonate DTBS : di-tert-butylsilyl

Et : ethyl

Imidt : trichloroacetimidate or N-phenyl trifluoroacetimidate

i_Pr _:_isopropyl

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-4- MPM : p-methoxyphenylmethyl MS : molecular sieves

NBS : N-bromosuccinimide NIS : N-iodosuccinimide

MNBA : 2-methyl-6-nitrobenzoic anhydride

Ph : phenyl

SE : 2-(trimethylsilyl)ethyl TBAF : n-tetrabutylammonium fluoride TBDPS : tert-butyldiphenylsilyl

TEA : triethylamine TES : triethylsilyl

Tf : trifluoromethanesulfonyl TFA : trifluoroacetic acid

TIPDS : tetraisopropyldisiloxyanylidene TIPS : triisopropylsilyl

TMEDA : tetramethylethylenediamine TMS : trimethylsilyl

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-5- ⥴ゝ ᆅ⌫ୖ࡟Ꮡᅾࡍࡿࠊࡍ࡭࡚ࡢ⏕ࡁ࡜ࡋ⏕ࡅࡿࡶࡢࡣࠕ᰾㓟ࠖࠊࠕࢱࣥࣃࢡ㉁ࠖࠊࠕ⢾㙐ࠖࡢ ୕ࡘࡢ㙐࡟ᨭ࠼ࡽࢀ࡚࠸ࡿࠋࡑࡋ࡚ࠊࡇࢀࡽࡑࢀࡒࢀࡢᶵ⬟ࡀ」㞧࡟㛵୚ࡋྜ࠺ࡇ࡜࡛ࠊ ⏕࿨ࢆ⥔ᣢࡋ࡚࠸ࡿࠋ⌧ᅾࠊࡇࢀࡽࡣ⏕࿨⛉Ꮫࡢ◊✲ᑐ㇟ࡢ୺㍈࡜࡞ࡗ࡚࠾ࡾࠊ✀ࠎࡢ⏕ ࿨⌧㇟ゎ᫂࡬ࡢ⣒ཱྀ࡜࡞ࡗ࡚࠸ࡿࠋ ⏕࿨⛉Ꮫ࡜ࡣࠊࠕ⏕࿨ࡢ௙⤌ࡳࠖࢆゎ᫂ࡍࡿࡇ࡜ࡀ┠ⓗࡢᏛၥ࡛࠶ࡾࠊ1970 ᖺ௦࡟࢘࢖ࣝ ࢫࢤࣀ࣒ࡢึゎㄞࡀ㐩ᡂࡉࢀ࡚௨᮶ࠊࢤࣀ࣒◊✲࡜࡜ࡶ࡟ᛴ㏿࡟Ⓨᒎࡋࡓࠋࡑࡋ࡚ࠊ1990 ᖺ௦࡟㛤ጞࡉࢀࡓࣄࢺࢤࣀ࣒ィ⏬ࡀ᏶஢ࡍࡿ2000 ᖺ௦࡟⮳ࡿࡲ࡛ࠊࠕ᰾㓟ࠖࠊࠕࢱࣥࣃࢡ㉁ࠖ ࡢ◊✲ࡀὀ┠ࢆᾎࡧ࡚࠸ࡓࠋࡋ࠿ࡋࠊ࣏ࢫࢺࢤࣀ࣒᫬௦࡜࡞ࡗࡓ⌧ᅾࠊᵝࠎ࡞ゎᯒᢏ⾡࡟ ࡼࡾࠊࢱࣥࣃࢡ㉁ࡢാࡁࡔࡅ࡛ࡣㄝ᫂ࡀ௜࠿࡞࠸ᵝࠎ࡞⏕࿨⌧㇟࡟ࠕ⢾㙐ࠖࡀ῝ࡃ㛵୚ࡋ ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚ࡁࡓࠋࡑࡋ࡚ࠊࠕ⢾㙐ࠖࡀࠕ᰾㓟ࠖࠊࠕࢱࣥࣃࢡ㉁ࠖ࡜୪ࡪ➨୕ ࡢ⏕࿨㙐࡛࠶ࡿࡇ࡜ࡀᗈࡃ▱ࡽࢀࡿࡼ࠺࡟࡞ࡗࡓࠋ ⢾㙐ࡣࠊᡃࠎ࡟࡜ࡗ࡚᭱ࡶ㌟㏆࡞ศᏊࡢ୍ࡘ࡜ゝ࠼ࡿ࡯࡝㌟ࡢᅇࡾ࡟Ꮡᅾࡍࡿࠋ౛࠼ࡤࠊ ẖ᪥㣗࡭ࡿࡈ㣤ࡣࢢࣝࢥ࣮ࢫࡀ α(1→4)⤖ྜ࡛㔜ྜࡋࡓ࢔࣑࣮ࣟࢫࡸD(1→4)⤖ྜཬࡧD (1→6)⤖ྜ࡛㔜ྜࡋࡓ࢔࣑ࣟ࣌ࢡࢳࣥࢆ୺ᡂศ࡜ࡋ࡚࠸ࡿࠋࡲࡓࠊẖ᪥౑࠺ᐇ㦂ࣀ࣮ࢺࡣࢢ ࣝࢥ࣮ࢫࡀE-(1→4)⤖ྜࡋࡓࢭ࣮ࣝࣟࢫ࠿ࡽฟ᮶࡚࠸ࡿࠋࡑࢀࡔࡅ࡛ࡣ࡞ࡃࠊᡃࠎࡢ⏕యෆ ࡛ࡣࠊࢱࣥࣃࢡ㉁ࡸ⬡㉁࡜⤖ྜࡋࡓ」ྜ⢾㉁࡜ࡋ࡚⣽⬊⾲㠃ୖ࡟Ꮡᅾࡋࠊ࣍ࣝࣔࣥ࡞࡝ࡢ ⏕⌮άᛶ≀㉁ࡸ⣽⳦ࠊ࢘࢖ࣝࢫࡢཷᐜయࠊ⣽⬊᥋╔ศᏊ࡞࡝ࡢᵝࠎ࡞ᙺ๭ࢆᢸࡗ࡚࠾ࡾࠊ ศᏊ㸫⣽⬊㛫࠾ࡼࡧ⣽⬊㸫⣽⬊㛫ࡢ┦஫ㄆ㆑ཬࡧ᝟ሗఏ㐩࡟῝ࡃ㛵୚ࡍࡿࠕ⣽⬊ࡢ㢦ࠖ࡜ ࡋ࡚ࠊ⏕࿨άື࡟࠾࠸࡚㠀ᖖ࡟㔜せ࡞ാࡁࢆࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊᵝࠎ࡞ᶵ⬟ࢆ᭷ࡍࡿ ⌮⏤࡜ࡋ࡚ࠊ⢾㙐ࡣྠ୍ࡢ⏕≀✀࡟࠾࠸࡚ࡶࠊჾᐁࡸ⤌⧊ࠊ⣽⬊࡟ࡼࡾࡑࢀࡒࢀ␗࡞ࡿࠊ 㠀ᖖ࡟ከᵝ࡞ᵓ㐀ࢆᣢࡘࡇ࡜ࡀ୍ࡘࡢせᅉ࡜ࡋ࡚⪃࠼ࡽࢀࡿࠋᵓ㐀ࡢከᵝᛶࡣࠊ⢾㙐ࢆᵓ ᡂࡍࡿ༢⢾ࡀ」ᩘࡢ཯ᛂⅬࢆᣢࡕࠊࢢࣜࢥࢩࢻ⤖ྜࢆ௓ࡋ࡚ᵝࠎ࡞ᵓ㐀ࢆᵓ⠏ࡍࡿࡇ࡜࠿

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-6- ࡽ⏕ࡲࢀ࡚࠸ࡿࠋࡑࡢ୍᪉࡛ࠊࡇࡢ」㞧࡞ᵓ㐀࡜ࠊࡑࢀ࡟ຍ࠼ࠊ⏕యෆ࡟࠾࠸࡚ᚤ㔞ᡂศ ࡛࠶ࡾධᡭࡀ㞴ࡋ࠸ࡇ࡜ࡀࠊ᰾㓟ࡸࢱࣥࣃࢡ㉁࡟ẚ࡭࡚◊✲ࡀ㐜ࢀࢆྲྀࡗ࡚࠸ࡿ୍ᅉ࡜࡞ ࡗ࡚࠸ࡿࠋࡑࢀᨾࠊ⢾㙐ࡣࠊࡲࡔゎ᫂ࡉࢀ࡚࠸࡞࠸㔜せ࡞ᶵ⬟ࡀᩘከࡃᏑᅾࡍࡿྍ⬟ᛶࢆ ⛎ࡵ࡚࠾ࡾࠊࡑࡢᶵ⬟ゎ᫂ࡀ་Ꮫࡸ⏕≀Ꮫศ㔝ࡢ᭦࡞ࡿⓎᒎ࡟⧅ࡀࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ ࡋ࡞ࡀࡽࠊኳ↛࡟࠾࠸࡚ᚤ㔞ᡂศ࡛࠶ࡿ⢾㙐ࡢᶵ⬟ゎ᫂ࢆ⾜࠺ࡓࡵ࡟ࡣࠊᶆရࡢᏳᐃ౪⤥ ࡀ୙ྍḞ࡜࡞ࡗ࡚ࡃࡿࠋࡑࡢ㝿ࠊ㠀ᖖ࡟᭷ຠ࡜࡞ࡿᡭἲࡀࠊ⢾㙐ࡢ᭷ᶵ໬Ꮫⓗྜᡂ࡟ࡼࡿ ౪⤥࡛࠶ࡿࠋ ⢾㙐ࡢ᭷ᶵ໬Ꮫⓗྜᡂ࡛ࡣࠊ⢾࡜⢾ࢆ⧅ࡄࢢࣜࢥࢩࢻ⤖ྜࢆᙧᡂࡍࡿࠊࢢࣜࢥࢩࣝ໬཯ ᛂࡀ㘽࡜࡞ࡿࠋࡇࡢ཯ᛂࢆ⧞ࡾ㏉ࡍࡇ࡜࡛ࠊ」㞧࡞⢾㙐ࢆᵓ⠏ࡋ࡚࠸ࡃࠋࡋ࠿ࡋࠊඛ࡯࡝ ࡶ㏙࡭ࡓࡼ࠺࡟⢾ࡣ」ᩘࡢ཯ᛂⅬࢆᣢࡘࡓࡵࠊࢢࣜࢥࢩࣝ໬཯ᛂࡢ㝿࡟ࠊ఩⨨␗ᛶయࠊཬ ࡧ❧య␗ᛶయࢆᙧᡂࡍࡿࠋ⌧ᅾࠊ఩⨨␗ᛶయ࡟㛵ࡋ࡚ࡣࠊỈ㓟ᇶࡢ཯ᛂᛶࡢᕪࡸಖㆤᇶࢆ ⏝࠸ࡿࡇ࡜࡛ࠊṤ࡝ࡢࢢࣜࢥࢩࣝ໬཯ᛂ࡟࠾࠸࡚ไᚚྍ⬟࡜࡞ࡗ࡚࠸ࡿࠋ୍᪉࡛ࠊ❧యไ ᚚࡣࠊ࢔ࣀ࣐࣮ຠᯝࡸ⁐፹ຠᯝࠊ࢔ࢩࣝ⣔ಖㆤᇶࢆ⏝࠸ࡓ㞄᥋ᇶຠᯝࡀ୍⯡ⓗ࡟⏝࠸ࡽࢀ ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࢀࡽࡣ୍ᐃࡢ㑅ᢥᛶࢆ♧ࡍࡶࡢࡢࠊ཯ᛂᇶ㉁ࡢᵓ㐀ࠊ⬺㞳ᇶ࡜άᛶ໬ ๣ࡢ⤌ࡳྜࡏ࡞࡝࡟ࡼࡾᙳ㡪ࡉࢀࡿ➼ࡢၥ㢟Ⅼࡀṧࡉࢀ࡚࠾ࡾࠊ᏶඲࡞❧య㑅ᢥᛶࡀᚓࡽ ࢀࡿࡇ࡜ࡣ⛥࡛࠶ࡿࠋࡲࡓࠊ㑅ᢥᛶࢆⓎ⌧ࡉࡏࡿ᮲௳ୗ࡛ࡣࠊᇶ㉁ࡢ⁐ゎᛶࡢపୗࠊ౑⏝ ࡛ࡁࡿಖㆤᇶࡀไ㝈ࡉࢀࡿ➼ࡢၥ㢟ࡀࡋࡤࡋࡤ⏕ࡌࡿࠋࡑࡢࡓࡵࠊຠ⋡ⓗ࡞ྜᡂᡓ␎ࢆ❧ ᱌ࡍࡿࡓࡵ࡟ࡣࠊ❧యไᚚἲࡢᣑ඘ࡀᚲ㡲࡜࡞ࡗ࡚ࡃࡿࠋ ㏆ᖺࠊࡇࢀࡽࡢ᪉ἲ࡟௦ࢃࡿ᪂ࡋ࠸❧యไᚚἲࡀᵝࠎ㛤Ⓨࡉࢀ࡚࠸ࡿࠋ౛࠼ࡤࠊCrich ࡽ ࡣD-ࢺࣜࣇ࣮ࣞࢺࢆ௓ࡋࡓE-࣐ࣥࣀࢩࣝ໬1_{ࢆሗ࿌ࡋࠊྜᡂ㞴᫆ᗘࡢ㧗࠸E-࣐ࣥࣀࢩࢻࢆᚓ}

ࡿࡇ࡜ࢆ㐩ᡂࡋ࡚࠸ࡿࠋࡲࡓࠊDemchenko ࡽࡀሗ࿌ࡋࡓࠊpicolinyl ᇶཬࡧ picolinoyl ᇶࢆ⏝ ࠸ࡓ❧య㑅ᢥⓗࢢࣜࢥࢩࣝ໬2_ࡸࠊ_{Boons ࡽࡀሗ࿌ࡋࡓࠊ2 ఩Ỉ㓟ᇶ࡟୙ᩧ⿵ຓᇶࢆᑟධࡋࡓ}

1_{D. Crich, S. Sun,}_{J. Org. Chem.}_11996,₆₁_{, 4506-4507.}

2_{a) J. T. Smoot, P. Pornsuriyasak, A. V. Demchenko,}_{Angew. Chem. Int. Ed.}_22005,₄₄_,

7123-7126.

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-7- ⢾౪୚యࢆ⏝࠸ࡓ᪉ἲ3_{ࡀሗ࿌ࡉࢀ࡚࠾ࡾࠊࡑࢀࡒࢀ⢾㙐ྜᡂ࡬ࡢ᭷⏝ᛶࡶド᫂ࡉࢀ࡚࠸ࡿ}4_ࠋ ࡇࡢࡼ࠺࡟ࠊ᪂ࡓ࡞❧యไᚚἲࡢ㛤Ⓨࡣࠊ」㞧࡞⢾㙐ࢆຠ⋡ⓗ࡟ᵓ⠏ࡍࡿࡇ࡜࡬ࡢ኱ࡁ ࡞ᡭຓࡅ࡜࡞ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ⢾⬡㉁ྜᡂ࡟᭷⏝࡞ࠊ᪂ࡋ࠸❧య㑅ᢥⓗࢢࣜࢥࢩ ࣝ໬཯ᛂࢆ㛤Ⓨࡋࠊ⢾㙐ྜᡂ࡟࠾ࡅࡿ❧యไᚚἲࡢ㑅ᢥ⫥ࡢᣑ඘ࢆ┠ᣦࡍࡇ࡜࡜ࡋࡓࠋ ➨୍㒊࡛ࡣࠊ2,3-⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓ 1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࢻ໬ࡢ᳨ウ࡟ࡘ࠸ ࡚ࠊ➨஧㒊࡛ࡣࠊ➨୍㒊࡛㛤Ⓨࡋࡓ᪉ἲࢆ฼⏝ࡋࡓE-ࢢࣜࢭࣟ⢾⬡㉁ྜᡂ࡟ࡘ࠸࡚㏙࡭ࡿࠋ c) J. P. Yasomanee, A. V. Demchenko, Chem. Eur. J. 22015, 21, 6572-6581.

3_{J. -H. Kim, H. Yang, G. -J. Boons,}_{Angew. Chem. Int. Ed.}_22005,₄₄_{, 947-949.} 4_{a) T. J. Boltje, J. -H. Kim, J. Park, G. -J. Boons,}_{Nat. Chem.}_22010,₂_{, 552-557.}

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-8-

➨

➨୍㒊

2,3-⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓ 1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࢻ໬ࡢ᳨ウ ➨୍❶ ⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍⠇ ⎔≧ಖㆤ⢾౪୚యࢆ⏝࠸ࡓ❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬཯ᛂ࡟㛵ࡍࡿ◊✲౛ ๓㏙ࡋࡓࡼ࠺࡟ࠊࡇࢀࡲ࡛࡟ᵝࠎ࡞❧యไᚚἲࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡇࡢ୰࡛ࡶࠊ㏆ᖺࠊ ࣋ࣥࢪࣜࢹࣥᇶࠊ⎔≧࣮࢝࣎ࢿ࣮ࢺᇶࠊ⎔≧࣮࢝ࣂ࣓࣮ࢺᇶࠊࢩࣜࣝ⣔ಖㆤᇶ࡜࠸ࡗࡓ⎔ ≧ಖㆤᇶࢆ⏝࠸࡚⢾ࡢ⎔ᵓ㐀ࢆᅛᐃࡋࡓࠊ஧⎔ᛶ⢾౪୚య࡟ࡼࡿ❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬ ཯ᛂࡀሗ࿌ࡉࢀ࡚࠸ࡿ (FFig. 1)ࠋCrich ࡽࡣࠊD-ࢺࣜࣇ࣮ࣞࢺࢆ௓ࡋࡓE-࣐ࣥࣀࢩࣝ໬1_࡟

࠾࠸࡚ࠊ࣐ࣥࣀ࣮ࢫࡢ4,6 ఩Ỉ㓟ᇶࡀ࣋ࣥࢪࣜࢹࣥᇶ࡛ᅛᐃ໬ࡉࢀࡿࡇ࡜࡛ࡡࡌࢀṍࡳࡀ⏕ ࡌࠊࡑࡢṍࡳࡀ୰㛫యᙧᡂ࡟࠾࠸࡚E-㑅ᢥᛶⓎ⌧࡟᭷ຠ࡟ാ࠸࡚࠸ࡿࡇ࡜5_{ࢆሗ࿌ࡋࡓࠋࡲ} ࡓࠊࢢࣝࢥ࣮ࢫᆺ౪୚య࡟㛵ࡋ࡚ࡣࠊ2,3 ఩Ỉ㓟ᇶࢆ࣮࢝࣎ࢿ࣮ࢺᇶ࡛ಖㆤࡋࡓ⢾౪୚య6_࡟ ࡼࡿ❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡇࡕࡽࡶྠᵝ࡟D-ࢺࣜࣇ࣮ࣞࢺࢆ⤒⏤ࡋࡓ E-(1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࢻ໬࡛࠶ࡿࡀࠊࢢࣝࢥ࣮ࢫࡢ 3,4 ఩Ỉ㓟ᇶࢆ࣮࢝࣎ࢿ࣮ࢺᇶ ࡛ಖㆤࡋࡓ౪୚యࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࡣ㑅ᢥᛶࡢపୗࡀࡳࡽࢀࡓࡇ࡜࠿ࡽࠊ࢔ࣀ࣐࣮఩ ௜㏆ࡢỈ㓟ᇶࢆᅛᐃࡍࡿࡇ࡜ࡀ㑅ᢥᛶⓎ⌧࡟኱ࡁࡃᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ ᭦࡟ࠊ3,4 ఩ࢆࣈࢱࣥ-2,3-ࣅࢫ࢔ࢭࢱ࣮࡛ࣝಖㆤࡋࡓ⢾౪୚య7_{࡛ࡣࠊ୰㛫యᙧᡂ᫬ࡢ࣓ࢺ} ࢟ࢩᇶࡢ❧యⓗ࡞┦஫స⏝ࡀE-㑅ᢥᛶⓎ⌧࡟㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ ࡇࡢࡼ࠺࡟ࠊ⎔≧ಖㆤᇶ࡟ࡼࡿ㓄ᗙࡢᅛᐃࡀࠊ⢾⎔ࡢᰂ㌾ᛶࢆไ㝈ࡋࠊࢢࣜࢥࢩࣝ໬཯ ᛂ࡟࠾ࡅࡿ୰㛫యࢆ࠶ࡿ୍ᐃࡢ㓄ᗙࢆඃඛⓗ࡟ᙧᡂࡉࡏࡿാࡁࡀ࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ ࡚ࡁࡓࠋࡲࡓࠊ࢔࣑ࣀ⢾࡟㛵ࡋ࡚ࡣࠊ2,3 ఩ࢆ࣮࢝ࣂ࣓࣮ࢺᇶ࡛ಖㆤࡋࡓ⢾౪୚య8_ࡸN_-࣋

5_{a) H. H. Jensen, L. U. Nordstrøm, M. Bols,}_{J. Am. Chem. Soc.}_22004,₁₂₆_{, 9205-9213.}

b) D. Crich, N. S. Chandrasekera, Angew. Chem. Int. Ed. 22004, 43, 5386-5389.

6_{D. Crich, P. Jayalath,}_{J. Org. Chem.}_22005,₇₀_{, 7252-7259.}

7_{D. Crich, V. Subramanian, T. K. Hutton,}_Tetrahedron_22007,₆₃_{, 5042-5049.} 8_{K. Benakili, C. Zha, R. J. Kerns,}_{J. Am. Chem. Soc.}_22001,₁₂₃_{, 9461-9462.}

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-9- ࣥࢪ࣮ࣝ࢝ࣂ࣓࣮ࢺᇶ࡛ಖㆤࡋࡓ⢾౪୚య9_{ࢆ⏝࠸ࡿࡇ࡜࡛ࠊྜᡂ㞴᫆ᗘࡢ㧗࠸ࠊ}_E-(1,2-_cis_-) ࢔࣑ࣀࢢࣜࢥࢩࢻࢆඃඛⓗ࡟ᙧᡂࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ≉࡟ࠊN-࣋ࣥࢪ࣮ࣝ࢝ࣂ࣓ ࣮ࢺᇶ࡛ಖㆤࡋࡓ⢾౪୚య࡟࠾࠸࡚ࡣࠊ㓟ᛶ᮲௳ୗ࡟࠾࠸࡚ᐜ᫆࡟E-య࠿ࡽD-య࡬࡜␗ᛶࡍ ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚࠾ࡾࠊࡇࢀࡣࣆࣛࣀ࣮ࢫ⎔࡜2,3 ఩ࡢ࣮࢝ࣂ࣓࣮ࢺᇶ࡟ࡼࡿ⦰⎔ᙧ ᡂ࡟ࡼࡾ⏕ࡌࡿṍࡳ࢚ࢿࣝࢠ࣮ࡀཎືຊ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀィ⟬໬Ꮫ࡟ࡼࡾゎ᫂ࡉࢀ࡚࠸ ࡿ10_{ࠋࡲࡓࠊ࢞ࣛࢡࢺ࣮ࢫཬࡧ࢞ࣛࢡࢺࢧ࣑ࣥ࡟㛵ࡋ࡚ࡣᙜ◊✲ᐊ࡛㛤Ⓨࡉࢀࡓ}_{4,6 ఩࡟⎔} ≧ࢩࣜࣝ⣔ಖㆤᇶ࡛࠶ࡿ DTBS ᇶࢆᑟධࡋࡓ⢾౪୚య11_{ࢆ⏝࠸ࡿࡇ࡜࡛ࠊDTBS ᇶࡢᔞ㧗} ࡉ࡟ࡼࡾࠊ㧗࠸1,2-cis-㑅ᢥᛶࢆᚓࡿࡇ࡜ࡀฟ᮶ࡿࠋ᭦࡟ࠊ㏆ᖺ࡛ࡣࠊ⎔≧ಖㆤᇶ࡟ࡼࡾ㓄 ᗙࢆኚ᥮ࡋࡓ⢾౪୚యࢆ⏝࠸ࡓ❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬࡜ࡋ࡚ࠊ2,3 ఩ࢆo-Xylylene ᇶ࡛ಖ ㆤࡋࡓࣇࣛࣀ࣮ࢫᆺ౪୚య12_{࡟ࡼࡿE-࢔ࣛࣅࣀࣇࣛࣀࢩࣝ໬ࠊ2,4 ఩ࢆ DTBS ᇶ࡛ᯫᶫࡋࠊ} 1_C₄_{㓄ᗙ࡬࡜ኚ᥮ࡋࡓࢢࣝࢡࣟࣥ㓟}13_{ࢆ⏝࠸ࡓE-ࢢࣝࢡࣟࢽࣝ໬ࠊࡲࡓࠊ3,6 ఩ࢆ}_o_-Xylylene ᇶ࡛ᯫᶫࡋ1S₃_{㓄ᗙ࡬࡜ኚ᥮ࡋࡓࢢࣝࢥ࣮ࢫ౪୚య}14_{ࢆ⏝࠸ࡓE-ࢢࣝࢥࢩࣝ໬࡞࡝ࡀሗ࿌ࡉ} ࢀ࡚࠸ࡿࠋ ௨ୖࡢሗ࿌౛࠿ࡽࡶࢃ࠿ࡿࡼ࠺࡟ࠊ⎔≧ಖㆤᇶࡀࢢࣜࢥࢩࢻ໬཯ᛂ࡟࠾ࡅࡿ❧య㑅ᢥᛶ ࡟ከ኱࡞ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚ࡁࡓࠋࡇࢀࡽࡢሗ࿌ࡢ୰࡛ࡶ≉࡟ࠊᮏ◊ ✲࡛ࡣࠊCrich ࡽ࡟ࡼࡿ 2,3 ఩ࢆ࣮࢝࣎ࢿ࣮ࢺᇶ࡛ಖㆤࡋࡓ⢾౪୚య࡟╔┠ࡋࡓࠋࡇࡢࡼ࠺ ࡟ࠊ2,3 ఩Ỉ㓟ᇶࢆ⎔≧ಖㆤᇶ࡛ᯫᶫࡍࡿࡇ࡜࡛ࢢࣝࢥ࣮ࢫཬࡧ࢞ࣛࢡࢺ࣮ࢫ࡟ࡶ㐺⏝࡛ࡁ ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡓࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ࢔ࣀ࣐࣮఩㏆ഐࡢ2,3 ఩Ỉ㓟ᇶࢆ⎔≧ಖㆤ

9_{S. Manabe, K. Ishii, Y. Ito,}_{J. Am. Chem. Soc.}_22006,₁₂₈_{, 10666-10667.}

10_{a) H. Satoh, J. Hutter, H. P. Lüthi, S. Manabe, K. Ishii, Y. Ito,}_{Eur. J. Org. Chem.}

2009, 1127-1131.

b) H. Satoh, S. Manabe, Y. Ito, H. P. Lüthi, T. Laino, J. Hutter, J. Am. Chem. Soc. 22011, 133, 5610-5619.

11_{a) A. Imamura, H. Ando, S. Korogi, G. Tanabe, O. Muraoka, H. Ishida, M. Kiso,}

Tetrahedron Lett. 22003, 44, 6725‒6728.

b)A. Imamura, A. Kimura, H. Ando, H. Ishida, M. Kiso, Chem. Eur. J. 22006, 12, 8862̼8870.

12_{A. Imamura, T. L. Lowary,}_{Org. Lett.}_22010,₁₂_{, 3686-3689.}

13_{T. Furukawa, H. Hinou, S. -I. Nishimura,}_{Org. Lett.}_22012,₁₄_{, 2102-2105.}

14_{Y. Okada, N. Asakura, M. Bando, Y. Ashikaga, H. Yamada,}_{J. Am. Chem. Soc.}_22012,

(13)

-10-

ࡋࡓ஧⎔ᛶ⢾౪୚యࢆࢆ⏝࠸ࡓࠊ᪂ࡋ࠸❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬ࡢ㛤Ⓨࢆ┠ᣦࡍࡇ࡜࡜ࡋ ࡓࠋ

(14)

-11- ➨஧⠇ ⎔≧ࢩࣜࣝ⣔ಖㆤᇶࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ༞ᴗ◊✲࡟࠾࠸࡚ࠊࢢࣝࢥ࣮ࢫ2,3 ఩Ỉ㓟ᇶࢆ⎔≧ࢩࣜࣝ⣔ಖㆤᇶ࡛࠶ࡿ TIPDS ᇶ࡛ಖ ㆤࡋࡓ⢾౪୚య11 ࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ࡜ࡇࢁࠊEtCN/CH2Cl2=2/1 ࡢΰྜ⁐ ፹୰࡟࠾࠸࡚㧗࠸ 1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ (SScheme 1)15_ࠋࡋ࠿ ࡋࠊప ࡟࠾ࡅࡿ⢾౪୚య 1 ࡢ⁐ゎᛶࡢᝏࡉ࡟ࡼࡾࠊ཰⋡ࡀ୰⛬ᗘ࡛࠶ࡿࡇ࡜ࡀㄢ㢟࡜ࡋ ࡚ṧࡿ⤖ᯝ࡜࡞ࡗࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ2,3 ఩ࢆ⎔≧ಖㆤࡋࡓ஧⎔ᛶ⢾౪୚యࡢ᭷⏝ᛶࢆ༑ศ ᮇᚅฟ᮶ࡿ⤖ᯝࡣᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊᘬࡁ⥆ࡁ஧⎔ᛶ⢾౪୚య࡟╔┠ ࡋࠊ2,3 ఩Ỉ㓟ᇶࢆᵝࠎ࡞኱ࡁࡉࡢ⎔≧ಖㆤᇶ࡛ಖㆤࡋࡓ஧⎔ᛶ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩ ࢻ໬཯ᛂ࡟࠾ࡅࡿ❧య㑅ᢥᛶࡢ᭦࡞ࡿ᳨ドࢆ⾜࠸ࠊ⢾⬡㉁ྜᡂ࡬฼⏝ྍ⬟࡞❧యไᚚἲࡢ ☜❧ࢆ┠ᣦࡍࡇ࡜࡜ࡋࡓࠋ Scheme 1 15_{ඵ⚄ ࡞࡯Ꮚ}_{ᒱ㜧኱Ꮫᛂ⏝⏕≀⛉Ꮫ㒊㣗ရ⏕࿨⛉Ꮫㄢ⛬ ༞ᴗㄽᩥ}_{, 22012.}

(15)

-12- ➨஧❶ ஧⎔ᛶ⢾౪୚యࡢྜᡂ ࡣࡌࡵ࡟ࠊᮏ◊✲࡟࠾࠸࡚⏝࠸ࡿ✀ࠎࡢ஧⎔ᛶ⢾౪୚యࡢྜᡂࢆ⾜ࡗࡓ (SScheme 2)ࠋࡲ ࡎࠊ஬ဨ⎔ࢆ᭷ࡍࡿDTBS ᆺ౪୚యࡢྜᡂࢆヨࡳࡓࠋࢢࣝࢥ࣮ࢫㄏᑟయ 4 ࢆฟⓎ≀㉁࡜ࡋ DTBS(OTf)2ࠊ2,6-Lutidine ࢆస⏝ࡉࡏࠊ2,3 ఩Ỉ㓟ᇶࡢ DTBS ໬ࢆ⾜ࡗࡓࠋࡋ࠿ࡋࠊ⢭〇 ࡢẁ㝵࡛DTBS ᇶࡢ㛤⿣࡟ࡼࡾ໬ྜ≀ 6 ࡬࡜ኚ໬ࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࡢࡼ࠺࡟໬ྜ ≀5 ࡀ㠀ᖖ࡟୙Ᏻᐃ࡛࠶ࡿ⌮⏤࡜ࡋ࡚ࠊ2,3 ఩Ỉ㓟ᇶ࡟࠾࠸࡚஬ဨ⎔࡜ࡢ⦰⎔ᵓ㐀ࢆᙧᡂࡍ ࡿࡇ࡜࡛ࡦࡎࡳࡀ⏕ࡌࡿࡇ࡜ࡀཎᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡇ࡜࠿ࡽࠊDTBS ᆺ౪୚య ࢆࢢࣜࢥࢩࢻ໬཯ᛂࡢ᳨ウ࡟⏝࠸ࡿ஦ࡣᅔ㞴࡜⪃࠼ࡓࠋ୍᪉࡛ࠊ୐ဨ⎔ࢆ᭷ࡍࡿTIPDS ᆺ ౪୚య9ࠊඵဨ⎔ࢆ᭷ࡍࡿo-Xylylene ᆺ౪୚య 12 ࡟࠾࠸࡚ࡣࠊࢢࣝࢥ࣮ࢫㄏᑟయ 4 ࢆฟⓎ ≀㉁࡜ࡋ࡚ࠊ2,3 ఩Ỉ㓟ᇶࡢ⎔≧ಖㆤᇶࡢᑟධࠊPhBCl2ࠊTriethylsilane ࢆ⏝࠸ࡓ࣋ࣥࢪࣜ ࢹࣥᇶࡢ㑏ඖ㛤⿣ࠊBn ᇶࡢᑟධࢆ⾜࠸ࠊࡑࢀࡒࢀⰋዲ࡞཰⋡࡟࡚ྜᡂࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ ᭦࡟ࠊ஑ဨ⎔ᵓ㐀ࢆᙧᡂࡍࡿ m-Xylylene ᆺ౪୚య 13 ࡢྜᡂࢆヨࡳࡓࡀࠊศᏊ㛫࡛ m-Xylylene ᇶࡀᯫᶫࡋࡓ஧㔞యࡢ⏕ᡂࡀ☜ㄆࡉࢀࠊ┠ⓗ≀㉁ࢆᚓࡿࡇ࡜ࡣฟ᮶࡞࠿ࡗࡓࠋ ࡇࡢࡇ࡜࠿ࡽࠊࢢࣝࢥ࣮ࢫ2,3 ఩Ỉ㓟ᇶ࡛ࡢ஑ဨ⎔௨ୖࡢ⎔ᵓ㐀ᙧᡂࡣ㠀ᖖ࡟㞴ࡋ࠸ࡇ࡜ࡀ ⪃࠼ࡽࢀࡓࠋࡲࡓࠊභဨ⎔⎔≧ಖㆤࢆࡋࡓBDA ᆺ౪୚య 15 ࡟㛵ࡋ࡚ࡣࠊ໬ྜ≀ 14 ࢆฟⓎ ≀㉁࡜ࡋ࡚⏝࠸ࠊButane-2,3-dioneࠊ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒యࠊTrimethyl orthoformate ࢆస⏝ࡉࡏࡿࡇ࡜࡛ྜᡂࢆ⾜ࡗࡓࠋ

(16)

-13- Scheme 2

(17)

-14-

➨୕❶ ஧⎔ᛶ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ

➨୍❶࡟࡚ྜᡂࡋࡓࠊභဨ⎔࠿ࡽඵဨ⎔ࢆ᭷ࡍࡿ⢾౪୚యࠊẚ㍑࡜ࡋ࡚㠀⎔≧ಖㆤ⢾౪ ୚య࡛࠶ࡿdi-Bn ᆺ౪୚య 116ࠊdi-TIPS ᆺ౪୚య 17 ࢆ⏝࠸ࠊNIS/TfOH Ꮡᅾୗࠊࢪࢡࣟࣟ ࣓ࢱࣥ⁐፹୰࡟࡚ࡑࢀࡒࢀࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࢆTable 1 ࡟♧ࡋࡓࠋEntry 1 ࠿ࡽ 8 ࡢ⤖ᯝࡼࡾࠊභဨ⎔࠿ࡽඵဨ⎔ࢆ᭷ࡍࡿ⢾౪୚యࢆ⏝࠸ࡓሙྜࠊ඲࡚࡟࠾࠸࡚

1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓࠊẚ㍑࡜ࡋ࡚ࠊ-80

ºC ࡟࠾࠸࡚㠀⎔≧ಖㆤ౪୚య࡛࠶ࡿ di-Bn ᆺ౪୚యࠊdi-TIPS ᆺ౪୚యࢆ⏝࠸ࡓሙྜ࡛ࡣ (Entry 9, 10)ࠊࡑࢀࡒࢀD/E = 14/86ࠊD/E = 58/42 ࡜ྠ ᗘ࡛ࡢ TIPDS ᆺ౪୚యࠊo-Xylylene ᆺ౪୚యࢆ⏝࠸ࡓሙྜࡢ1,2-trans-㑅ᢥᛶࡼࡾࡶప࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ ࡞࠾ࠊBDA ᆺ౪୚ య࡟㛵ࡋ࡚ࡣࠊ-80 ºC ࡛ࡣ཯ᛂࡢ㐍⾜ࡀ㠀ᖖ࡟㐜ࡃࠊᅄ᪥㛫཯ᛂࢆ⥅⥆ࡉࡏࡓࡀࠊ౪୚యࡣ ᏶඲࡟ᾘ㈝ࡋ࡞࠿ࡗࡓ (Entry 1)ࠋࡑࡇ࡛ࠊ-40 ºC ࡟᪼ ࡋ࡚཯ᛂࢆ⾜ࡗࡓ⤖ᯝࠊ཯ᛂࡣ㐍⾜ࡋࠊྠ ᗘ࡛ࡢTIPDS ᆺ౪୚యࠊo-Xylylene ᆺ౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ࡜ẚ㍑ ࡋ࡚ྠ⛬ᗘࡢ㑅ᢥᛶࡀᚓࡽࢀࡓࠋࡲࡓࠊTIPDS ᆺ౪୚యࠊo-Xylylene ᆺ౪୚య࡟㛵ࡋ࡚ࡣࠊ ཯ᛂ ᗘࡀୖ᪼ࡍࡿ࡜ࠊ㑅ᢥᛶࡀపୗࡍࡿࡇ࡜࠿ࡽࠊ1,2-trans-㑅ᢥᛶⓎ⌧࡟ࡣ཯ᛂ ᗘࡀ ᙳ㡪ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡾࠊ1,2-trans-ࢢࣜࢥࢩࢻࡢᙧᡂࡣ⇕ຊᏛⓗ࡟ไᚚࡉࢀ࡚࠸ࡿࡇ ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊࢺࣛࣥࢫᆺࡢࣅࢩࢼࣝࢪ࣮࢜ࣝ࡟࠾࠸࡚ࠊBDA ᆺ౪୚యࡀᙧᡂࡍ ࡿභဨ⎔ᵓ㐀ࡣሀ∼࡛࠶ࡿࡀᨾࠊᖹ㠃ᵓ㐀ࢆ࡜ࡿ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࢆᙧᡂ ࡍࡿ㝿࡟࢚ࢿࣝࢠ࣮ࡀᚲせ࡛࠶ࡿࡓࡵࠊప ࡛ࡣάᛶ໬ࡀ㉳ࡇࡾ࡟ࡃࡃࠊ཯ᛂࡢ㐍⾜ࡀ㠀 ᖖ࡟㐜ࡃ࡞ࡗࡓࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ

(18)

-15- TTable 1

(19)

-16- ➨ᅄ❶ ඵဨ⎔⎔≧ಖㆤࡋࡓ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍⠇ 2,3-o-Xylylene ᆺ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍㡯 4,6 ఩Ỉ㓟ᇶಖㆤᇶ࡟ࡼࡿᙳ㡪ࡢ᳨ド ➨஧❶ࡢ⤖ᯝࡼࡾࠊභ࠿ࡽඵဨ⎔ࢆ᭷ࡍࡿ⢾౪୚యࢆ⏝࠸ࡿࡇ࡜࡛ࠊ1,2-trans-㑅ᢥⓗ ࡟ࢢࣜࢥࢩࢻ໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ⥆࠸࡚ࡣࠊ⎔≧ಖㆤ౪୚యࢆ⏝࠸࡚ࠊ ᵝࠎ࡞཯ᛂ᮲௳࡟࠾ࡅࡿヲ⣽࡞᳨ドࢆ⾜࡞࠺ࡇ࡜࡜ࡋࡓࠋࡋ࠿ࡋࠊBDA ᆺ౪୚యࡣ཯ᛂࢆ 㐍⾜ࡉࡏࡿࡓࡵ࡟ࡣ㧗࠸ ᗘࡀᚲせ࡛࠶ࡾࠊ᭦࡟TIPDS ᆺ౪୚య࡟㛵ࡋ࡚ࡣࠊ࣋ࣥࢪࣜࢹ ࣥᇶࡢ㑏ඖ㛤⿣ࡢ㝿࡟TIPDS ᇶࡢ㛤⿣࡟ࡼࡿ๪⏕ᡂ≀ࡢ⏕ᡂࡀ☜ㄆࡉࢀࡓ16_{ࠋࡇࡢࡇ࡜࠿} ࡽࠊᵝࠎ࡞཯ᛂ᮲௳࡟࠾࠸࡚Ᏻᐃ࡛࠶ࡾࠊ౪୚య⏤᮶ࡢ๪⏕ᡂ≀ࡢ⏕ᡂࡀᑡ࡞࠸o-Xylylene ᆺ⢾౪୚యࢆ௨㝆ࡢヲ⣽࡞᳨ウ࡟⏝࠸ࡿࡇ࡜࡜ࡋࡓࠋ ࡲࡎࡣࠊ4,6 ఩Ỉ㓟ᇶಖㆤᇶࡢᙳ㡪ࡢ᳨ドࢆ⾜࡞ࡗࡓ (TTable 2)ࠋ4,6 ఩Ỉ㓟ᇶ࡟ Bn ᇶࠊ MPM ᇶࠊTBDPS ᇶࠊAc ᇶࢆᑟධࡋࡓ⢾౪୚య 23 ࠿ࡽ 28 ཬࡧ࢞ࣛࢡࢺ࣮ࢫᆺ౪୚య 29 ࢆࡑࢀࡒࢀ⏝࠸࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊEntry 1 ࡟࠾࠸࡚ࠊ4,6 ఩ࢆ MPM ᇶ࡛ಖㆤࡋࡓ౪୚యࢆ⏝࠸ࡓሙྜࠊBn ᇶ࡛ಖㆤࡋࡓ౪୚యࢆ⏝࠸ࡓሙྜ࡜ྠᵝ࡟㧗࠸ 1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡓࠋ୍᪉࡛ࠊ4 ఩ࠊ6 ఩Ỉ㓟ᇶࡢ࡝ࡕࡽ࠿୍᪉ࡲࡓࡣඹ࡟㟁Ꮚồ ᘬᇶ࡛࠶ࡿ Ac ᇶࢆᑟධࡋࡓ⢾౪୚యࢆ⏝࠸ࡓሙྜࠊ1,2-trans-㑅ᢥᛶࡀపୗࡍࡿࡇ࡜ࡀ᫂ ࡽ࠿࡜࡞ࡗࡓ (Entry 3, 5, 6)ࠋ࡞࠾ࠊ6 ఩࡟ TBDPS ᇶࢆᑟධࡋࡓ⢾౪୚యࢆ⏝࠸ࡓሙྜ (Entry 2) ࡟࠾࠸࡚ࡣࠊࢢࣜࢥࢩࢻ໬཯ᛂ୰ࠊD-ࢢࣜࢥࢩࢻ࡜E-ࢢࣜࢥࢩࢻࡢ⏕ᡂẚࡀኚ໬ ࡋࡓࡓࡵࠊ␗ᛶ໬཯ᛂࡀ㉳ࡇࡗ࡚࠸ࡿࡇ࡜ࡀ᥎ ࡉࢀࡓࠋࡇࡢ⌧㇟࡟㛵ࡍࡿ᳨ドࡣࠊ➨ᅄ ❶ ➨஬㡯࡟࡚ヲ⣽ࢆ㏙࡭ࡿࠋ⥆࠸࡚ࠊEntry 7 ࠿ࡽ 9 ࡛ࡣࠊ4 ఩Ỉ㓟ᇶࡢ㓄ྥ࡟ࡼࡿ㑅ᢥ ᛶ࡬ࡢᙳ㡪ࢆ᳨ドࡍࡿࡓࡵ࡟ࠊ࢞ࣛࢡࢺ࣮ࢫᆺ౪୚యࢆ⏝࠸࡚-80 ºC ࠿ࡽ 0 ºC ࡟࡚ࢢࣜࢥ ࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ࡝ࡢ཯ᛂ ᗘ࡟࠾࠸࡚ࡶࢢࣝࢥ࣮ࢫᆺ౪୚య12 ࢆ⏝࠸ࡓ 16_{ඵ⚄ ࡞࡯Ꮚ}_{ᒱ㜧኱Ꮫ኱Ꮫ㝔 ᛂ⏝⏕≀⛉Ꮫ◊✲⛉ ಟኈㄽᩥ}_{, 22015.}

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-17- ሙྜࡼࡾࡶ㑅ᢥᛶࡀపୗࡍࡿ࡜࠸࠺஦ࡀศ࠿ࡗࡓࠋࡲࡓࠊࢢࣝࢥ࣮ࢫᆺ౪୚య112 ࢆ⏝࠸ࡓ ሙྜ࡜ẚ㍑ࡋࠊ཯ᛂ ᗘࡢୖ᪼࡟క࠺㑅ᢥᛶࡢపୗࡀ㢧ⴭ࡛࠶ࡿࡇ࡜ࡶ☜ㄆࡉࢀࡓࠋ ௨ୖࡢ⤖ᯝࡼࡾࠊo-Xylylene ᆺ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ࡟࠾࠸࡚ࡣ཯ᛂ ᗘࠊ 4,6 ఩ࡢỈ㓟ᇶಖㆤᇶཬࡧ 4 ఩Ỉ㓟ᇶࡢ㓄ྥࡀ㑅ᢥᛶ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ ࡗࡓࠋ Table 2

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-18- ➨஧㡯 ⁐፹࡟ࡼࡿᙳ㡪ࡢ᳨ド ⥆࠸࡚ࠊࢢࣜࢥࢩࢻ໬཯ᛂ࡟⏝࠸ࡿ⁐፹ࡢᙳ㡪ࡢ᳨ドࢆ⾜࡞ࡗࡓ (TTable 3)ࠋࡲࡎࠊ Entry 1ࠊ2 ࡛ࡣࢺ࢚ࣝࣥཬࡧᅄሷ໬Ⅳ⣲ࢆ⏝࠸࡚ 0 ºC ࡟࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࠋ ࡑࡢ⤖ᯝࠊྠ ᗘࡢࢪࢡ࣓ࣟࣟࢱࣥ୰࡟࡚⾜ࡗࡓሙྜ࡜ྠ⛬ᗘࡢ1,2-trans-㑅ᢥᛶࡀᚓࡽ ࢀࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ0 ºC ࡟࠾࠸࡚ࡣࠊపᴟᛶ⁐፹ࡣ㑅ᢥᛶⓎ⌧࡟ᙳ㡪ࢆ୚࠼࡞࠸ࡇ࡜ ࡀ♧၀ࡉࢀࡓࠋ୍᪉ࠊEntry 3 ࡛ࡣࠊࣉࣟࣆ࢜ࢽࢺࣜࣝࢆ⏝࠸࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗ ࡓ࡜ࡇࢁࠊEntry 1 ࠿ࡽ Entry 2 ࡜ẚ㍑ࡋ࡚㧗࠸ 1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡓࠋࡇࢀࡣࠊ ࢽࢺࣜࣝ⁐፹ຠᯝ17_{࡟ࡼࡿ㑅ᢥᛶࡢྥୖ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋࠊ}_{-80 ºC ࡟࡚ࣉࣟࣆ}

࢜ࢽࢺࣜࣝࠊࢪࢡ࣓ࣟࣟࢱࣥ⁐፹ࡢΰྜ⁐፹ࢆ⏝࠸ࡓሙྜ (Entry 4) ࡛ࡣࠊࢪࢡ࣓ࣟࣟ ࢱࣥࡢࡳ⏝࠸ࡓሙྜ࡜ẚ㍑ࡋ࡚㑅ᢥᛶࡀపୗࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊEntry 5 ࡟࠾࠸ ࡚ࡣ࢚࣮ࢸࣝ⁐፹ຠᯝ18_࡟ࡼࡾ_1,2-_cis_{-ࢢࣜࢥࢩࢻࡀඃඛⓗ࡟⏕ᡂࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ}

17_{a) R. R. Schmidt, E. Rücker,}_{Tetrahedron Lett.}_11980,₂₁_{, 1421-1424.}

b) S. Hashimoto, M. Hayashi, R. Noyori, Tetrahedron Lett. 11984, 25, 1379-1382.

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-19- T Table 3 ➨୕㡯 ࣝ࢖ࢫ㓟ཬࡧ⬺㞳ᇶ࡟ࡼࡿᙳ㡪ࡢ᳨ド ḟ࡟ࠊ✀ࠎࡢࣝ࢖ࢫ㓟ࢆ⏝࠸࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ (TTable 4)ࠋࡲࡎࠊEntry 1 ࠿ ࡽ3 ࡛ࡣࠊ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒యࢆ⏝࠸࡚཯ᛂࢆ⾜ࡗࡓࠋEntry 1 ࡛ࡣ NIS ࢆ1.5 ᙜ㔞ࠊ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒యࢆ 0.9 ᙜ㔞ຍ࠼ࡓ࡜ࡇࢁࠊ཰⋡ 69%ࠊ D/Eẚ 3/97 ࡜ TfOH ࢆ⏝࠸ࡓሙྜ (TTable 1, Entry 6) ࡜ྠᵝ࡟㧗࠸ 1,2-trans-㑅ᢥᛶࡀᚓࡽ ࢀࡓࠋࡇࡢ⤖ᯝ࠿ࡽࠊD-ࢺࣜࣇ࣮ࣞࢺయࡢ㛵୚ࡀ࡞ࡃ࡚ࡶ 1,2-trans-㑅ᢥᛶࡀⓎ⌧ࡍࡿࡇ࡜ ࡀࢃ࠿ࡗࡓࠋࡋ࠿ࡋࠊ๪⏕ᡂ≀࡜ࡋ࡚D-ࣇࢵ໬⢾ 37 ࡀ 33%ᚓࡽࢀࡓࠋ⥆࠸࡚ࠊEntry 2ࠊ3 ࡛ࡣࡑࢀࡒࢀ-40 ºCࠊ0 ºC ࡟࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊEntry 2ࠊ3 ඹ࡟ Entry 1 ࡜ྠᵝ࡟ TfOH ࢆ⏝࠸ࡓሙྜ (TTable 1, Entry 7, 8)ࡼࡾࡶ㑅ᢥᛶࡀྥୖࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋ ࡞࠾ࠊ0 ºC ࡟࠾࠸࡚ࡣD-ࣇࢵ໬⢾ 37 ࡢ⏕ᡂࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋḟ࡟ Entry 4 ࡛ࡣࠊ TMSOTf ࢆ⏝࠸ࡓ࡜ࡇࢁࠊTfOH ࢆ⏝࠸ࡓሙྜ (TTable 1, Entry 7) ࡜ẚ㍑ࡋⱝᖸࡢ㑅ᢥᛶ

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-20- ࡢྥୖࡀࡳࡽࢀࡓࠋ⥆࠸࡚ࠊEntry 5 ࡛ࡣ୰㛫య࡜ࡋ࡚D-ࢺࣜࣇࣝ࢖࣑ࢻࢆ⤒⏤ࡋࠊ 1,2-trans-⤖ྜࢆඃඛⓗ࡟ᙧᡂࡍࡿ࡜⪃࠼ࡽࢀࡿ Tf2NH19ࢆ⏝࠸࡚ࢳ࢜ࢢࣜࢥࢩࢻࡢάᛶ໬ ࢆヨࡳࡓࡀࠊ཯ᛂࡣ࡯࡜ࢇ࡝㐍⾜ࡋ࡞࠿ࡗࡓࠋEntry 6 ࡛ࡣ NOBF4ࢆ⏝࠸ࡓࡀࠊࡇࡢሙྜ ࡟࠾࠸࡚ࡶ཯ᛂࡢ㐍⾜ࡣぢࡽࢀ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊEntry 7ࠊ8 ࡛ࡣࠊNIS ࡜ゐ፹㔞ࡢ Tf2NH ࡲࡓࡣNOBF4ࢆ⏝࠸࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ࡜ࡇࢁࠊࡑࢀࡒࢀ୰⛬ᗘࡢ1,2-trans-㑅 ᢥᛶࡀᚓࡽࢀࡓࠋ࡞࠾ࠊEntry 8 ࡟࠾࠸࡚ࡣࠊ๪⏕ᡂ≀࡜ࡋ࡚D-ࣇࢵ໬⢾ 337 ࡀ 12%ᚓࡽࢀ ࡓࠋ᭦࡟ࠊEntry 9 ࡛ࡣࢪ࣓ࢳࣝࢪࢫࣝࣇ࢕ࢻࠊMeOTf ࢆ⏝࠸࡚⣔୰࡟࡚ DMTST ࢆ⏕ᡂ ࡉࡏ20_{ࠊ౪୚యࡢάᛶ໬ࢆヨࡳࡓࡀࠊ཯ᛂࡢ㐍⾜ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ୍᪉ࠊᕷ㈍ࡢ}_DMTSF ࢆ⏝࠸ࡓሙྜࠊ-40 ºC ࡛ࡣ཯ᛂࡢ㐍⾜ࡀ㠀ᖖ࡟㐜࠿ࡗࡓࡓࡵࠊ0 ºC ࡟᪼ ࡋࡓ࡜ࡇࢁ཯ᛂ ࡣ㐍⾜ࡋࡓࡀD/Eẚ 51/49 ࡜㑅ᢥᛶࡣᚓࡽࢀ࡞࠿ࡗࡓࠋ ௨ୖࡢ⤖ᯝࡼࡾD-ࢺࣜࣇ࣮ࣞࢺࡢ㛵୚ࡀ࡞ࡃ࡚ࡶ 1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓࠊTf2NHࠊNOBF4ࢆ⏝࠸ࠊ┤᥋౪୚యࢆάᛶ໬ࡍࡿࡇ

࡜ࡣฟ᮶࡞࠿ࡗࡓࡀࠊNIS ࡜⤌ࡳྜࢃࡏࡿࡇ࡜࡛ࠊTfOH ࢆ⏝࠸ࡓሙྜ࡜ྠ⛬ᗘࡢ 1,2-trans -㑅ᢥᛶࡀᚓࡽࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

19_{R. Arihara, S. Nakamura, S. Hashimoto,}_{Angew. Chem. Int. Ed.}_22005,₄₄_{, 2245-2249.} 20_{I. Ohtsuka, T. Ako, R. Kato, S. Daikoku, S. Koroghi, T. Kanemitsu, O. Kanie,}

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-21- T Table 4 ⥆࠸࡚ࡣ⬺㞳ᇶ࡟ࡼࡿᙳ㡪ࡢ᳨ドࢆ⾜ࡗࡓ (TTable 5)ࠋࡲࡎࠊࢺࣜࢡࣟࣟ࢔ࢭࢺ࢖࣑ࢹ࣮ ࢺᆺ౪୚య38 ࢆ⏝࠸࡚-80 ºC ࡟࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ (Entry 1, 2)ࠋࡑࡢ⤖ᯝࠊ TMSOTf ཬࡧ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒యࢆࣝ࢖ࢫ㓟࡜ࡋ࡚⏝࠸ࡓሙྜࡢ࡝ࡕࡽ ࡟࠾࠸࡚ࡶ㧗࠸཰⋡ཬࡧ1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡓࠋࡲࡓࠊ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝ ࢸࣝ㘒యࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࡶࣇࢵ໬⢾ࡢ⏕ᡂࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋࡋ࠿ࡋࠊࢺࣜࢡࣟ

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-22- ࣟ࢔ࢭࢺ࢖࣑ࢹ࣮ࢺᆺ౪୚య338 ࡣ㠀ᖖ࡟୙Ᏻᐃ࡛࠶ࡾࠊ༢㞳⢭〇᫬࡟࣑࣊࢔ࢭࢱ࣮ࣝయ࡟ ศゎࡋࡸࡍ࠸ࡓࡵࠊEntry 3ࠊ4 ࡛ࡣࡼࡾᏳᐃ࡞ࠊN-ࣇ࢙ࢽࣝࢺࣜࣇࣝ࢜ࣟ࢔ࢭࢺ࢖࣑ࢹ࣮ ࢺᆺ౪୚య21_{39 ࢆ⏝࠸ࡓࠋࡑࡢ⤖ᯝࠊTMSOTf ࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࠊⱝᖸࡢ㑅ᢥᛶࡢప} ୗࡀࡳࡽࢀࡓࡶࡢࡢࠊEntry 3ࠊ4 ඹ࡟㧗࠸཰⋡ཬࡧ 1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡓࠋ ௨ୖࡢ⤖ᯝࡼࡾࠊ౪୚యࡢㄪ〇ࡢ⡆౽ࡉ࠿ࡽࡶࠊN-ࣇ࢙ࢽࣝࢺࣜࣇࣝ࢜ࣟ࢔ࢭࢺ࢖࣑ࢹ ࣮ࢺᆺ౪୚య 39 ࢆ⏝࠸ࡿ᪉ࡀ㐺ࡋ࡚࠸ࡿ࡜⪃࠼ࠊ⥆ࡃཷᐜయ࡟ࡼࡿᙳ㡪ࡢ᳨ドࡣ N-ࣇ࢙ ࢽࣝࢺࣜࣇࣝ࢜ࣟ࢔ࢭࢺ࢖࣑ࢹ࣮ࢺᆺ౪୚య39 ࢆ⏝࠸ࡿࡇ࡜࡜ࡋࡓࠋ Table 5

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-23-

➨ᅄ㡯 ཷᐜయ࡟ࡼࡿᙳ㡪ࡢ᳨ド

⥆࠸࡚ࡣࠊࢳ࢜ࢢࣜࢥࢩࢻ 12 ཬࡧࠊ➨୕㡯࡟࡚⏝࠸ࡓ N-ࣇ࢙ࢽࣝࢺࣜࣇࣝ࢜ࣟ࢔ࢭࢺ ࢖࣑ࢹ࣮ࢺᆺ౪୚య39 ࢆ⏝࠸࡚ࠊ✀ࠎࡢཷᐜయ 40 ࠿ࡽ 48 ࡜ࡢࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ (TTable 6)ࠋࡲࡓࠊẚ㍑࡜ࡋ࡚ di-Bn ᆺ౪୚య 116 ࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂࡶ⾜ࡗࡓ (TTable 7)ࠋ

ࡲࡎo-Xylylene ᆺ౪୚య 12 ཬࡧ 39 ࢆ⏝࠸ࡓሙྜࠊ඲࡚࡟࠾࠸࡚ 1,2-trans-ࢢࣜࢥࢩࢻ ࢆඃඛⓗ࡟ᚓࡿ⤖ᯝ࡜࡞ࡗࡓࠋࡋ࠿ࡋࠊཷᐜయࡢᵓ㐀࡟ࡼࡾ㑅ᢥᛶࡢᕪࡀ⏕ࡌࡿࡇ࡜ࡀศ ࠿ࡗࡓࠋ౛࠼ࡤࠊEntry 1 ࠿ࡽ 3 ࡜ Entry 9 ࢆẚ㍑ࡋࡓሙྜࠊ୕⣭࢔ࣝࢥ࣮ࣝࢆ⏝࠸ࡓ Entry 9 ࡣ୍⣭࢔ࣝࢥ࣮ࣝ࡜ࡢࢢࣜࢥࢩࢻ໬཯ᛂࡢ⤖ᯝ࡜ྠ⛬ᗘ࡟㧗࠸㑅ᢥᛶࡀᚓࡽࢀࡓࠋࡇࡢࡇ ࡜࠿ࡽࠊ❧య㑅ᢥᛶࡣཷᐜయࡢỈ㓟ᇶࡢ཯ᛂᛶ࡟኱ࡁࡃᙳ㡪ࢆཷࡅ࡚࠸࡞࠸ࡇ࡜ࡀ♧၀ࡉ ࢀࡓࠋ୍᪉࡛⢾ཷᐜయࢆ⏝࠸ࡓሙྜ࡛ࡣࠊཷᐜయࡢಖㆤᵝᘧࡢࡳ␗࡞ࡿ⤌ࡳྜࢃࡏࡢEntry 4 ࡜ Entry 5 ࡲࡓࠊEntry 6 ࡜ Entry 7 ࡟࠾࠸࡚ࠊࡑࢀࡒࢀྠ⛬ᗘࡢ㑅ᢥᛶࡀᚓࡽࢀࡓࡇ࡜ ࠿ࡽࠊཷᐜయࡢỈ㓟ᇶࡢಖㆤᵝᘧࡶ኱ࡁࡃᙳ㡪ࢆ୚࠼࡚࠸࡞࠸࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋࠊEntry 4ࠊ5 ࡜ Entry 6ࠊ7 ࢆẚ㍑ࡋࡓሙྜࠊ4,6-diol ᆺཷᐜయࢆ⏝࠸ࡓ Entry 6ࠊ7 ࡢ᪉ࡀ㑅ᢥᛶ ࡢྥୖࡀࡳࡽࢀࡓࡇ࡜࠿ࡽࠊࢢࣜࢥࢩࢻ⤖ྜࢆᙧᡂࡍࡿ㝿ࠊ౪୚య࡜ཷᐜయࡀ᥋㏆ࡍࡿ㑄 ⛣≧ែࡢᵓ㐀ࡀ㑅ᢥᛶ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜᥎ ࡋࡓࠋࡲࡓࠊN-ࣇ࢙ࢽࣝࢺ ࣜࣇࣝ࢜ࣟ࢔ࢭࢺ࢖࣑ࢹ࣮ࢺᆺ౪୚య39 ࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࡶࠊάᛶ໬๣࡜ࡢ⤌ࡳྜࢃ ࡏ࡟ࡼࡿᕪࡣぢࡽࢀࡓࡶࡢࡢཷᐜయࡢ཯ᛂᛶ࡟ࡣ኱ࡁࡃᙳ㡪ࢆཷࡅ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ ḟ࡟ࠊ㠀⎔≧ಖㆤ౪୚య࡛࠶ࡿdi-Bn ᆺ౪୚య 16 ࡜ཷᐜయ 40 ࠿ࡽ 48 ࡜ࡢࢢࣜࢥࢩࢻ໬ ཯ᛂࡢ⤖ᯝࢆTable 7 ࡟♧ࡋࡓࠋ౛࠼ࡤཷᐜయ 47 ࢆ⏝࠸ࡓሙྜࠊo-Xylylene ᆺ౪୚య࡛ࡣ D/Eẚ 30/70 (TTable 6, Entry 8) ࡛࠶ࡿࡀࠊdi-Bn ᆺ౪୚య࡟࠾࠸࡚ࡣD/Eẚ 63/37 (TTable 7, Entry 8) ࡜D-ࢢࣜࢥࢩࢻࡀඃඛⓗ࡟⏕ᡂࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊo-Xylylene ᆺ౪୚యࢆ⏝

(27)

-24-

࠸ࡓሙྜࠊdi-Bn ᆺ౪୚యࢆ⏝࠸ࡓሙྜࡼࡾࡶྠ➼ (Entry 3, 6)ࠊࡲࡓࡣࡑࢀ௨ୖ (Entry 1, 2, 4, 5, 7, 8, 9) ࡢ㑅ᢥᛶࡀᚓࡽࢀࠊ⎔≧ಖㆤᇶࡀE-㑅ᢥᛶⓎ⌧࡟᭷ຠ࡛࠶ࡿࡇ࡜ࡀࡇࡢ⤖ᯝ ࡼࡾ♧၀ࡉࢀࡓࠋ

(28)

-25- T

(29)

-26- T Table 7 ➨஬㡯 ␗ᛶ໬཯ᛂ࡟㛵ࡍࡿ᳨ド ➨୍㡯࡟࠾࠸࡚ࠊ6 ఩࡟ TBDPS ᇶࢆᑟධࡋࡓ⢾౪୚య 24 ࢆ⏝࠸࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ ⾜ࡗࡓ࡜ࡇࢁ཯ᛂ୰ࠊ1,2-cis-ࢢࣜࢥࢩࢻ࡜ 1,2-trans-ࢢࣜࢥࢩࢻࡢ⏕ᡂẚࡀኚ໬ࡍࡿ⌧㇟ ࡀほᐹࡉࢀࡓ (TTable 2, Entry 2)ࠋFig. 2 ࡟཯ᛂ㏣㊧᫬ࡢ TLC ࢆ♧ࡋࡓࠋ཯ᛂ㛤ጞᚋ⣙ 2 ᫬㛫ᚋࡲ࡛ࡣ 1,2-cis-ࢢࣜࢥࢩࢻࡀඃඛⓗ࡟⏕ᡂࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࡀࠊࡑࡢᚋࠊ

1,2-trans-ࢢࣜࢥࢩࢻࡢ๭ྜࡀቑຍࡋࠊ9 ᫬㛫ᚋ࡟ࡑࡢ⏕ᡂẚࡢኚ໬ࡀぢࡽࢀ࡞ࡃ࡞ࡗࡓࠋ

ࡑࡢᚋࠊ཯ᛂ㛤ጞ࠿ࡽ17 ᫬㛫ᚋ࡟཯ᛂࢆ೵Ṇࡉࡏࡓ࡜ࡇࢁࠊD/Eẚ 4/96 ࡛ࢢࣜࢥࢩࢻࢆᚓ ࡓࠋ➨୍㡯࡟࡚✀ࠎࡢಖㆤᵝᘧࡢ⢾౪୚య࡜ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓࡀࠊࡇࡢࡼ࠺࡞⏕

(30)

-27-

ࡢ6-TBDPS ᆺ౪୚యࢆ⏝࠸࡚ヲ⣽࡞᳨ドࢆ⾜࠺ࡇ࡜࡜ࡋࡓ (TTable 8)ࠋࡲࡎࠊEntry 2 ࡛ ࡣࠊࣝ࢖ࢫ㓟ࢆ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒య࡟ኚ᭦ࡋ࡚཯ᛂࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ Entry 1 ࡜ྠᵝ࡟ 1,2-cis-ࢢࣜࢥࢩࢻ࡜ 1,2-trans-ࢢࣜࢥࢩࢻࡢ⏕ᡂẚࡢኚ໬ࡀࡳࡽࢀࠊ12 ᫬㛫ᚋ࡟ࡣ TLC ୖ࡟࡚ 1,2-cis-ࢢࣜࢥࢩࢻࡢ⏕ᡂࡀ☜ㄆࡉࢀ࡞ࡃ࡞ࡗࡓࠋࡋ࠿ࡋࠊ౪୚య ࡀ28%ṧᏑࡋࠊ᭦࡟๪⏕ᡂ≀࡛࠶ࡿࣇࢵ໬⢾ࡢ⏕ᡂ࡟ࡼࡾప཰⋡࡜࡞ࡗࡓࠋ⥆࠸࡚ࠊEntry 3 ࡛ࡣࠊ࢞ࣛࢡࢺ࣮ࢫᆺ౪୚య 67 ࢆ⏝࠸࡚཯ᛂࢆ⾜ࡗࡓࠋࡋ࠿ࡋࠊࢢࣝࢥ࣮ࢫᆺ౪୚య࡜ ࡣ␗࡞ࡾࠊ᫬㛫ࡢ⤒㐣࡟క࠺ࢢࣜࢥࢩࢻࡢ⏕ᡂẚࡢኚ໬ࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋ⥆࠸࡚ࠊEntry 4 ࡛ࡣ 2,3 ఩ࢆ TIPDS ᇶ࡛ಖㆤࡋࡓ౪୚య 68 ࡟࠾࠸࡚ࡶྠᵝ࡟཯ᛂࢆ⾜ࡗࡓࠋࡋ࠿ࡋࠊࡇ ࡕࡽࡶࢢࣜࢥࢩࢻࡢ⏕ᡂẚࡢኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ ௨ୖࡢ⤖ᯝࡼࡾࠊࡇࡢࡼ࠺࡞⌧㇟ࡣࠊ6 ఩ࢆ TBDPS ᇶ࡛ಖㆤࡋࡓo-Xylylene ᆺࢢࣝࢥ ࣮ࢫ౪୚య24 ࡢࡳ࡟⌧ࢀࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

(31)

-28- F

Fig. 2 ౪୚య 24 ࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ࡟࠾ࡅࡿ཯ᛂ㏣㊧ TLC

Table 8

␗ᛶ໬཯ᛂࡣexo 㛤⎔࡜ endo 㛤⎔ࡢ 2 ✀㢮ࡢ⤒㊰࡟࡚㉳ࡇࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ (FFig. 3)ࠋexo 㛤⎔ࡣ࢔ࣀ࣐࣮Ⅳ⣲࡜ࢢࣜࢥࢩࢻࢆᙧᡂࡋ࡚࠸ࡿ㓟⣲ࡢ㛫ࡢ⤖ྜࡀษ᩿ࡉࢀࠊ⎔≧

(32)

-29- ࢝ࢳ࢜ࣥࡀ⏕ᡂࡍࡿࠋ୍᪉࡛ࠊendo 㛤⎔ࡣ࢔ࣀ࣐࣮Ⅳ⣲࡜⎔ෆ㓟⣲ࡢ⤖ྜࡀษ᩿ࡉࢀ࡚㙐 ≧࢝ࢳ࢜ࣥࡀ⏕ᡂࡍࡿࠋ୍⯡ⓗ࡟ࠊࣆࣛࣀࢩࢻ࡟㛵ࡋ࡚ࡢ␗ᛶ໬཯ᛂࡣ exo 㛤⎔ࡀ࡯࡜ࢇ ࡝࡛࠶ࡿࡀࠊ┿㘠ࡽࡣ2,3-trans-N-࣋ࣥࢪ࣮ࣝ࢝ࣂ࣓࣮ࢺᇶࢆ᭷ࡍࡿ⢾࡟ᑐࡋ࡚ࠊ୕ࣇࢵ໬ ࣍࢘⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒యࢆస⏝ࡉࡏࡿ࡜endo 㛤⎔࡟ࡼࡿ␗ᛶ໬ࡀ㉳ࡇࡿࡇ࡜ࢆሗ࿌ࡋ ࡚࠸ࡿ 9_{ࠋ㓟ᛶ᮲௳ୗ࡟࠾࠸࡚ࠊ㙐≧ࡢ໬ྜ≀ࡢ⏕ᡂࡣぢࡽࢀ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊendo 㛤} ⎔࡛ࡣ࡞ࡃࠊexo 㛤⎔࡟ࡼࡿ␗ᛶ໬཯ᛂ࡛ࡣ࡞࠸࠿࡜᥎ ࡉࢀࡿࠋ⌧ẁ㝵࡛ࡣࠊ6 ఩ TBDPS ᇶࡀ᭷ຠ࡟ാࡃࡇ࡜௨እ࡟ᶵᵓゎ᫂ࡢᡭ᥃࠿ࡾ࡜࡞ࡿ⤖ᯝࡣᚓࡽࢀ࡚࠸࡞࠸ࡀࠊࡇࡢ⌧㇟ ࡣ㠀ᖖ࡟⯆࿡῝࠸⌧㇟ࡔ࡜⪃࠼ࡿࠋ௒ᚋࡣࠊ᭦࡟ヲ⣽࡞᳨ドཬࡧᶵᵓゎ᫂ࢆ⾜࠺஦࡛ࠊ᪂ ࡓ࡞❧య㑅ᢥⓗࢢࣜࢥࢩࢻ໬㛤Ⓨࡢ⣒ཱྀࢆぢฟࡍࡇ࡜ࡀฟ᮶ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼࡚࠸ࡿࠋ

Fig. 3 㓟ᛶ᮲௳ୗ࡛ࡢ exo 㛤⎔࡜ endo 㛤⎔

➨஧⠇ 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ⢾౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂ ➨୍㡯 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ౪୚యࡢྜᡂ࡜ࢢࣜࢥࢩࢻ໬཯ᛂ ࡇࢀࡲ࡛ࡢ⤖ᯝࡼࡾࠊo-Xylylene ᆺ౪୚యࢆ⏝࠸ࡿࡇ࡜࡛ࠊ1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩ ࢻ໬ࡀ㐍⾜ࡍࡿ࡜࠸࠺஦ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡋ࠿ࡋࠊo-Xylylene ᇶࡣ Bn ᇶ࡜㢮ఝࡢᵓ㐀ࢆ ᣢࡘࡓࡵࠊ㑅ᢥⓗ࡞o-Xylylene ᇶࡢ㝖ཤࡀᅔ㞴࡞ሙྜࡀ࠶ࡿࠋᚑࡗ࡚ࠊ௒ᚋࡢ⢾㙐ྜᡂ࡬ ࡢᛂ⏝ࢆど㔝࡟ධࢀࡿ࡜ࠊ㑅ᢥⓗ࡞㝖ཤࡀྍ⬟࡞⎔≧ಖㆤᇶࢆᑟධࡋࡓ⢾౪୚యࢆ⏝࠸ࡿ ᚲせࡀ࠶ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡟࠾࠸࡚ࡣࠊp-࣓ࢺ࢟ࢩ࣋ࣥࢪࣝᇶ࡜ྠᵝ࡟㓟໬ࡲࡓࡣᙉ㓟᮲ ௳ୗ࡟࡚㝖ཤྍ⬟࡞ 2,3 ఩Ỉ㓟ᇶࢆ 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝ (NDM) ᇶ࡛ಖㆤࡋࡓ౪୚య

(33)

-30- ࢆ⏝࠸ࡿࡇ࡜࡜ࡋࡓࠋ ࡲࡎࠊ2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢱࣀ࣮ࣝ 771 ࢆฟⓎ≀㉁࡜ࡋࠊ࢔ࢵ࣌ࣝ཯ᛂ࡟ࡼࡾ⮯⣲໬ࢆ⾜ ࠸ࠊ໬ྜ≀72 ࢆྜᡂࡋࡓ (SScheme 4)ࠋ⥆࠸࡚ࠊྜᡂࡋࡓ 72 ࢆ⏝࠸࡚ࠊ໬ྜ≀ 4 ࡢ 2,3 ఩ Ỉ㓟ᇶࡢ2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᇶࡢᑟධࠊ࣋ࣥࢪࣜࢹࣥᇶࡢ㑏ඖⓗ㛤⿣ࠊ6 ఩ Bn ໬ࢆ⤒ ࡚౪୚య75 ࢆᚓࡓ (SScheme 5)ࠋ Scheme 4 Scheme 5 ⥆࠸࡚ࠊᚓࡽࢀࡓ౪୚య75 ࢆ⏝࠸࡚ࠊ-80 ºC ࡟࡚ࢢࣜࢥࢩࢻ໬཯ᛂࢆ⾜ࡗࡓ (SScheme 6)ࠋ ࡑࡢ⤖ᯝࠊo-Xylylene ᆺ౪୚య࡜ྠᵝ࡟㧗཰⋡ཬࡧ㧗㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡍ ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

(34)

-31- Scheme 6 ➨஧㡯 2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᇶ㝖ཤࡢ᳨ウ ➨୍㡯࡟࡚ࠊ౪୚య75 ࢆ⏝࠸ࡿࡇ࡜࡛㧗࠸ 1,2-trans-㑅ᢥᛶࡀᚓࡽࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜ ࡞ࡗࡓࡢ࡛ࠊ⥆࠸࡚ࡣNDM ᇶࡢ㝖ཤࡢ᳨ウࢆ⾜ࡗࡓࠋಟኈㄽᩥ16_{࡟࠾࠸࡚ࠊ໬ྜ≀}_{77 ࢆ} ⏝࠸࡚ࠊNDM ᇶ㝖ཤࡢ᳨ウࢆ⾜ࡗࡓ⤖ᯝࠊTFA/Toluene = 10/1 ࡢΰྜ⁐፹୰22_{࡛཯ᛂࢆ⾜} ࡗࡓሙྜࠊ཰⋡Ⰻࡃ㝖ཤࢆ⾜࠺ࡇ࡜ࡀฟ᮶ࡿࡇ࡜ࢆሗ࿌ࡋࡓ (TTable 9, Entry 33)ࠋ Table 9 ࡋ࠿ࡋࠊ⢾㙐ྜᡂ࡟ᗈࡃ㐺⏝ࡍࡿࡓࡵ࡟ࡣࠊࡼࡾ✜ࡸ࠿࡞཯ᛂ᮲௳࡛ࡢ㝖ཤࢆ⾜࠺ᚲせࡀ

(35)

-32- ࠶ࡿ࡜⪃࠼ࡓࠋࡑࡇ࡛ࠊDDQ ࢆ⏝࠸ࡓ୰ᛶ᮲௳ୗ࡛ࡢ㝖ཤࡢ᳨ウࢆ⾜࠺ࡇ࡜࡜ࡋࡓ (TTable 10)ࠋࡲࡎࠊEntry 1 ࡛ࡣࠊCH2Cl2/H2O=18/1 ࡢΰྜ⁐፹୰࡟࡚ DDQ ࢆస⏝ࡉࡏࡓ23ࠋࡑ ࡢ⤖ᯝࠊฟⓎཎᩱ࡛࠶ࡿ໬ྜ≀75 ࡣ࡯࡜ࢇ࡝ᾘ㈝ࡉࢀࡓࡀࠊ」ᩘࡢ㧗ᴟᛶࡢ⏕ᡂ≀ࡀ⏕ᡂ ࡋࡓࡇ࡜ࢆTLC ୖ࡟࡚☜ㄆࡋࡓࠋ⢭〇ࢆ⾜ࡗࡓ⤖ᯝࠊ┠ⓗ≀࡛࠶ࡿ໬ྜ≀ 79 ࡣࠊࢃࡎ࠿ 3%ࡋ࠿ᚓࡿࡇ࡜ࡀฟ᮶ࡎࠊ๪⏕ᡂ≀࡜ࡋ࡚ࠊ2 ఩ࠊ3 ఩ཬࡧ 4 ఩ࡀỈ㓟ᇶ࡜࡞ࡗࡓ໬ྜ≀ 80 ࢆ 11%༢㞳ࡋࡓࠋ࡞࠾ࠊࡑࡢ௚ࡢ⏕ᡂ≀ࡣ༢㞳⢭〇ࡀᅔ㞴࡛࠶ࡗࡓࡓࡵࠊᵓ㐀ࢆỴᐃࡍ ࡿ ࡇ ࡜ ࡀ ฟ ᮶ ࡞ ࠿ ࡗ ࡓ ࠋ ⥆ ࠸ ࡚ ࠊEntry 2 ࡛ ࡣ ࠊ DDQ ࡢ ᙜ 㔞 ࢆ ῶ ࡽ ࡋ ࠊ CH2Cl2/MeOH/H2O=4/1/Trace ࡢΰྜ⁐፹୰࡟࡚཯ᛂࢆ⾜ࡗࡓ24ࠋࡑࡢ⤖ᯝࠊ┠ⓗ≀ࡢ཰⋡ ࡣ12%࡟ྥୖࡋࡓࡶࡢࡢࠊEntry 1 ࡜ྠᵝ࡟」ᩘࡢ๪⏕ᡂ≀ࡀ⏕ᡂࡋࠊ᭦࡟ฟⓎཎᩱࢆ 40% ᅇ཰ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋEntry 3 ࡛ࡣࠊ⁐፹⣔ࢆ CH2Cl2/ MeOH =4/1 ࡢΰྜ⁐፹୰࡟࡚཯ ᛂࢆ⾜ࡗࡓ࡜ࡇࢁࠊ┠ⓗ໬ྜ≀79 ࡣ 21%ࡲ࡛ྥୖࡋࡓࠋࡋ࠿ࡋࠊEntry 1 ཬࡧ 2 ࡜ྠᵝ࡟ 」ᩘࡢ⏕ᡂ≀ࡢ⏕ᡂࡀ☜ㄆࡉࢀࠊ4 ఩ࡀỈ㓟ᇶ࡜࡞ࡗࡓ໬ྜ≀ 81ࠊ4 ఩ 6 ఩࡜ࡶ࡟Ỉ㓟ᇶ ࡜࡞ࡗࡓ໬ྜ≀82 ࡢ⏕ᡂࢆ☜ㄆࡋࡓࠋࡲࡓࠊEntry 4 ࡣ SnCl2ࠊTMSClࠊAnisole ࢆ⏝࠸ࡓ 25_{ࡀࠊࡇࡢሙྜ࡟࠾࠸࡚ࡶ」ᩘࡢ⏕ᡂ≀ࡀ⏕ᡂࡋࡓࠋESI-MS ࡟ࡼࡾࠊ┠ⓗ≀㉁ࡢศᏊ㔞ࡣ} ☜ㄆ࡛ࡁࡓࡀࠊ⑞㊧㔞⛬ᗘ࡛࠶ࡗࡓࠋEntry 5 ࡛ࡣࠊSnCl4ࠊPhSH ࢆ⏝࠸ࡓ26ࡀࠊࡇࡕࡽ ࡶྠᵝ࡟┠ⓗ≀ࢆᚓࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ ௨ୖࡢ⤖ᯝࡼࡾࠊDDQ ࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࠊ4 ఩ཬࡧ 6 ఩ࡢ Bn ᇶࡀ㝖ཤࡉࢀࡓ๪⏕ ᡂ≀ࡀከࡃ⏕ᡂࡋࡓࡇ࡜࠿ࡽࠊ⏝࠸ࡿᇶ㉁ࡢ4,6 ఩Ỉ㓟ᇶಖㆤᇶࢆኚ᭦ࡋ࡚෌ᗘ᳨ウࢆヨࡳ ࡿࡇ࡜࡜ࡋࡓࠋ

23_{Y. Oikawa, T. Yoshioka, O. Yonemitsu,}_{Tetrahedron Lett.}_11982,₂₃_{, 885-888.}

24_{J. Xia, S. A. Abbas, R. D. Locke, C. F. Piskorz, J. L. Alderfer, E. L. Matta,}_Tetrahedron

Lett. 22000, 41, 169-173.

25_{T. Akiyama, H. Shima, S. Ozaki,}_Synlett_{11992, 415-416.}

(36)

-33- T

Table 10

Fig. 4 ᚓࡽࢀࡓ๪⏕ᡂ≀

⥆࠸࡚ࡣࠊ᳨ウ࡟⏝࠸ࡿᇶ㉁ࡢ4,6 ఩Ỉ㓟ᇶಖㆤᇶࢆ Ac ᇶ࡟ኚ᭦ࡋ࡚ NDM ᇶ㝖ཤࡢ᳨ ウࢆ⾜ࡗࡓ (TTable 11)ࠋࡲࡎࠊEntry 1 ࡛ࡣࠊTable 10, Entry 1 ࡜ྠᵝ࡟ CH2Cl2/H2O=18/1

ࡢΰྜ⁐፹୰࡟࡚཯ᛂࢆ⾜ࡗࡓ࡜ࡇࢁࠊ๪⏕ᡂ≀ࡢ⏕ᡂࡀῶᑡࡋࠊ཰⋡ 60%࡜୰⛬ᗘࡢ཰

⋡࡟࡚┠ⓗ≀ࢆᚓࡿࡇ࡜ࡀฟ᮶ࡓࠋ⥆࠸࡚ࠊEntry 2 ࡛ࡣࠊTable 10 ࡟࡚᭱ࡶ㧗཰⋡࡛࠶ࡗ ࡓCH2Cl2/ MeOH =4/1 ࡢΰྜ⁐፹୰࡟࡚཯ᛂࢆ⾜ࡗࡓ⤖ᯝࠊEntry 1 ࡜ྠ⛬ᗘࡢ཰⋡࡟࡚

(37)

-34- ┠ⓗ≀ࢆᚓࡓࠋ᭦࡟Entry 3 ࡛ࡣࠊ㓑㓟ࢆຍ࠼ࡓ27_{࡜ࡇࢁࠊ཰⋡ࡣ}_{69%ࡲ࡛ྥୖࡋࡓࠋࡲࡓࠊ} Entry 4 ࡛ࡣࠊࣂࢵࣇ࢓࣮ࢆຍ࠼28_{ࠊ୰ᛶ᮲௳ୗ࡟࡚཯ᛂࢆ⾜ࡗࡓࡀࠊ཰⋡ࡣ}_{19%࡟࡜࡝ࡲ} ࡗࡓࠋ௨ୖࡢ⤖ᯝࡼࡾࠊ୰⛬ᗘࡢ཰⋡࡟࡚┠ⓗ≀ࢆᚓࡿࡇ࡜ࡣ࡛ࡁࡓࡀࠊࡇࢀ௨ୖࡢ཰⋡ ࡢྥୖࡣᅔ㞴ࡔ࡜⪃࠼ࡓࠋ ௨ୖࡼࡾࠊDDQ ࢆ⏝࠸ࡓሙྜࠊ㝖ཤࡣྍ⬟࡛࠶ࡿࡀ୰⛬ᗘࡢ཰⋡࡜࡞ࡗࡓࡓࡵࠊ TFA/Toluene ΰྜ⁐፹ࢆ⏝࠸ࡿ᮲௳ࡀ᭱㐺࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ T Table 11

27_{H. Lee, R. G. Harvey,}_{J. Org. Chem.}_11988,₅₃_{, 4587-4589.}

(38)

-35- ➨஬❶ NMR ཬࡧᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸ࡓ⎔≧⢾౪୚యࡢᵓ㐀ゎᯒ ➨୍⠇ NMR ࢆ⏝࠸ࡓ⎔≧ಖㆤ⢾౪୚యࡢ㓄ᗙゎᯒ ➨୍❶࠿ࡽ➨୕❶ࡲ࡛ࡢᵝࠎ࡞᳨ド࡟࠾࠸࡚ࠊ2,3 ఩Ỉ㓟ᇶ࡟⎔≧ಖㆤᇶࢆᑟධࡋࡓ⢾౪ ୚యࢆ⏝࠸ࡿࡇ࡜࡛ࠊ1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ ࡓࠋᮏ❶࡛ࡣࠊࡇࡢࡼ࠺࡟1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡋࡓ࣓࢝ࢽࢬ࣒࡟㛵 ࡋ࡚ゎ᫂ࢆ⾜ࡗࡓࠋ ᮏ◊✲࡟࠾࠸࡚ࠊ1,2-trans-㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡋࡓ⌮⏤࡜ࡋ࡚ࠊ1) 2, 3 ఩ ⎔≧ಖㆤᇶࡢᔞ㧗ࡉ࡟ࡼࡿ❧య㞀ᐖࠊ2) ⢾౪୚యࡢ㓄ᗙ࡟ࡼࡿᙳ㡪ࠊ3) ࢜࢟ࢯ࢝ࣝ࣋ࢽ࢘ ࣒࢖࢜ࣥ୰㛫యࡢ㓄ᗙ࡟ࡼࡿᙳ㡪 ࡢ୕Ⅼࡀ⪃࠼ࡽࢀࡓࠋࡲࡎࠊ୍Ⅼ┠ࡢ 2, 3 ఩⎔≧ಖㆤᇶ ࡢᔞ㧗ࡉ࡟ࡼࡿ❧య㞀ᐖ࡟㛵ࡋ࡚ࡣࠊ➨஧❶࡛ࡢ BDA ᆺ౪୚యࠊTIPDS ᆺ౪୚యࠊ o-Xylylene ᆺ౪୚యࢆ⏝࠸ࡓࢢࣜࢥࢩࢻ໬཯ᛂࡢ⤖ᯝ (TTable 1)ࡼࡾࠊࡇࡢ୰࡛᭱ࡶᔞ㧗࠸ ࡜TIPDS ᆺ౪୚య࡜ o-Xylylene ᆺ౪୚యࡢ㑅ᢥᛶࡀ࡝ࡢ཯ᛂ ᗘ࡟࠾࠸࡚ࡶ࡯࡜ࢇ࡝ྠ ࡌ࡛࠶ࡗࡓࡇ࡜ࠊࡲࡓࠊTIPDS ᆺ౪୚య࡜ྠᵝ࡟ᔞ㧗࠸࡜⪃࠼ࡽࢀࡿ㠀⎔≧ಖㆤ౪୚య࡛ ࠶ࡿTIPS ᆺ౪୚య࡛ࡣ 1,2-cis-యࡀඃඛⓗ࡟⏕ᡂࡋࡓࡇ࡜࠿ࡽ 2,3 ఩⎔≧ಖㆤᇶࡢᔞ㧗ࡉ ࡣ㑅ᢥᛶⓎ⌧࡟኱ࡁࡃᙳ㡪ࡋ࡚࠸࡞࠸࡜⪃࠼ࡽࢀࡿࠋ⥆࠸࡚ࠊ஧Ⅼ┠ࡢ⢾౪୚యࡢ㓄ᗙ࡟ ࡼࡿᙳ㡪࡟㛵ࡋ࡚ࡣࠊࡑࢀࡒࢀࡢ⢾౪୚యࡢ1 ఩࠿ࡽ 5 ఩ࡢࣉࣟࢺࣥࡢ⤖ྜᐃᩘࢆẚ㍑ࡋ ࡓ⤖ᯝ (TTable 12)ࠊ㠀⎔≧ಖㆤ౪୚య࡛࠶ࡿ di-Bn ࡜ࡢ኱ࡁ࡞ᕪࡣぢࡽࢀࡎࠊ⢾౪୚య⮬ యࡢ㓄ᗙࡢṍࡳ࡟ࡼࡿᙳ㡪ࡣ࡞࠸࡜⪃࠼ࡽࢀࡿࠋ

(39)

-36- T Table 12 ࡲࡓࠊ୕Ⅼ┠ࡢ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢ❧య㓄ᗙ࡟ࡼࡿᙳ㡪࡟㛵ࡋ࡚ࡣࠊ཯ᛂ ᗘࡀ㑅ᢥᛶⓎ⌧࡟኱ࡁࡃᙳ㡪ࢆ୚࠼࡚࠸ࡿࡇ࡜ࠊỈ㓟ᇶಖㆤᇶࠊ4 ఩ࡢỈ㓟ᇶࡢ㓄ྥ࡟ࡼ ࡾ㑅ᢥᛶࡀኚ໬ࡍࡿࡇ࡜࠿ࡽࠊ⢾౪୚య⮬య࡛ࡣ࡞ࡃࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫య 㓄ᗙࡢ❧య㓄ᗙࡀ㑅ᢥᛶ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫య࡟╔┠ࡋࠊࡑࡢ❧య㓄ᗙゎᯒࢆヨࡳࡿࡇ࡜࡜ࡋࡓࠋ ୍⯡ⓗ࡟ࠊࢢࣜࢥࢩࣝ໬཯ᛂࡣ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫య⤒⏤ࡋࡓồ᰾⨨᥮཯ᛂ ࡛࠶ࡿ࡜ࡉࢀ࡚࠸ࡿ (SScheme 7)ࠋࡋ࠿ࡋࠊ㘽࡜࡞ࡿ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡣᑑ ࿨ࡀ10-12_{⛊௨ୗ࡜㠀ᖖ࡟▷ࡃ୙Ᏻᐃ࡛࠶ࡾࠊ┤᥋ⓗ࡟ᤊ࠼ࡓ౛ࡣᮍࡔሗ࿌ࡉࢀ࡚࠸࡞࠸ࠋ} ࡋ࠿ࡋ㏆ᖺࠊWoerpel ࡽ29_{ࡣࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢࣔࢹࣝ໬ྜ≀࡜ࡋ࡚࢜࢟} ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥSbCl6ሷࢆྜᡂࡋࠊ1H NMR ࡟ࡼࡿ㓄ᗙゎᯒࢆ⾜ࡗࡓࡇ࡜ࢆሗ࿌ࡋ

29_{a) S. Chamberland, J. W. Ziller, K. A. Woerpel,}_{J. Am. Chem. Soc.}_22005,₁₂₇_,

5322-5323.

(40)

-37- ࡓࠋࡲࡓࠊ2016 ᖺ࡟ࡣ Blériot ࡽ30_{ࡣࠊ㉸㓟ࡢ}_HF/SbF₅_ࢆ⏝࠸࡚_{2-ࢹ࢜࢟ࢩࢢࣝࢥࣆࣛࣀ} ࣮ࢫཬࡧ2-ࣈࣟࣔࢢࣝࢥࣆࣛࣀ࣮ࢫࡢࢢࣜࢥࢩࣝ࢝ࢳ࢜ࣥࣔࢹࣝࢆྜᡂࡋࠊ1_{H NMR ࡟ࡼ} ࡿ㓄ᗙゎᯒࢆ⾜ࡗࡓࡇ࡜ࢆሗ࿌ࡋࡓࠋࡇࡢࡼ࠺࡟ࠊ┤᥋ⓗ࡟࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰ 㛫యࢆ࡜ࡽ࠼ࡿࡇ࡜ࡣ㞴ࡋ࠸ࡶࡢࡢࠊᏳᐃ࡞ࣔࢹࣝ໬ྜ≀ࡢྜᡂ࡟ᡂຌࡋࡓࡇ࡜࡛ࠊࢢࣜ ࢥࢩࣝ໬཯ᛂ࡟࠾ࡅࡿ❧య㑅ᢥᛶⓎ⌧ࡢ࣓࢝ࢽࢬ࣒ࢆࡼࡾᐇ㦂໬Ꮫⓗ࡟ㄝ᫂ࡍࡿࡇ࡜ࡀྍ ⬟࡟࡞ࡗࡓࠋࡑࡇ࡛ᮏ◊✲࡟࠾࠸࡚ࡣࠊゎᯒ࡟⏝࠸ࡿ౪୚యࡢಖㆤᇶࡢᏳᐃᛶࡢほⅬ࠿ࡽࠊ Woerpel ࡽࡀሗ࿌ࡋࡓ᪉ἲࢆ⏝࠸࡚࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢࣔࢹࣝ໬ྜ≀ࢆྜ ᡂࡋࠊࡑࡢ㓄ᗙゎᯒࢆヨࡳࡿࡇ࡜࡜ࡋࡓࠋ S Scheme 7 ࡲࡎࡣࠊࣔࢹࣝ໬ྜ≀ࡢྜᡂࢆヨࡳࡓࠋo-Xylylene ᆺ౪୚య 12 ࢆฟⓎ≀㉁࡜ࡋࠊ⬺ࣇ࢙ ࢽࣝࢳ࢜໬ࢆ⾜ࡗࡓᚋ࡟ࠊDess-Martin 㓟໬࡟ࡼࡾࣛࢡࢺࣥయ 86 ࡬࡜ᑟ࠸ࡓࠋࡑࡋ࡚ࠊࣛ ࢡࢺࣥయ࡟ᑐࡋ࡚Et3OSbCl6ࢆస⏝ࡉࡏ࡚ࣔࢹࣝ໬ྜ≀87 ࡢྜᡂࢆヨࡳࡓ (TTable 13)ࠋ

30_{A. Martin, A. Arda, J. Désiré, A. Martin-Mingot, N. Probst, P. Sinaÿ, J.}

(41)

-38- Scheme 8 Table 13 ࡲࡎࠊEnrty 1 ࡛ࡣࠊࢼࢫࣇࣛࢫࢥࢆ⏝࠸ࠊ㔜ࢪࢡ࣓ࣟࣟࢱࣥ࡟໬ྜ≀ 86 ࢆ⁐ゎᚋࠊヨ⸆ ࢆຍ࠼ࠊ-80 ºC ࡛ 2 ᫬㛫᧠ᢾࡋࠊNMR ࢳ࣮ࣗࣈ࡟཯ᛂᾮࢆ⛣ࡋ࡚-80 ºC ࡟࡚1_{H NMR ࢆ} ᐃࡋࡓࠋࡋ࠿ࡋࠊ཯ᛂࡣ㐍⾜ࡋ࡚࠾ࡽࡎࠊ໬ྜ≀87 ࡢ⏕ᡂࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋ཯ᛂࡀ 㐍⾜ࡋ࡞࠿ࡗࡓཎᅉ࡜ࡋ࡚ヨ⸆ࡢศゎࡀ⪃࠼ࡽࢀࡓࡓࡵࠊEntry 2 ࡛ࡣࠊ-80 ºC ࡟෭༷ࡋ ࡓ࣓ࢱࣀ࣮ࣝࣂࢫ୰࡟࡚ࠊணࡵヨ⸆ࢆධࢀࡓNMR ࢳ࣮ࣗࣈ࡟㔜ࢪࢡ࣓ࣟࣟࢱࣥ࡟⁐ゎࡋࡓ ໬ྜ≀86 ࢆ࢟ࣕࢽ࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾຍ࠼࡚-80 ºC ࡟࡚1_{H NMR ࢆ ᐃࡋࡓࠋࡋ࠿ࡋࠊ} Entry 1 ࡜ྠᵝ࡟ኚ໬ࡀぢࡽࢀ࡞࠿ࡗࡓࡓࡵࠊ ᐃ ᗘࢆᚎࠎ࡟᪼ ࡋࠊほᐹࢆ⾜ࡗࡓࠋࡑ ࡢ⤖ᯝࠊᐊ ࡲ࡛᪼ ࡋࡓ࡜ࡇࢁࠊ」ᩘࡢ⏕ᡂ≀ࡢ⏕ᡂࡀ☜ㄆࡉࢀࡓࠋ⥆࠸࡚Entry 3 ࡛ ࡣᐊ ࡟࡚Entry 2 ࡜ྠᵝࡢ᪉ἲ࡛ NMR ࢳ࣮ࣗࣈ࡟཯ᛂᾮࢆຍ࠼ࠊࡲࡎࡣࠊ0 ºC ࡟࡚1_H NMR ࢆ ᐃࡋࡓࠋࡑࡢ⤖ᯝࠊ ᐃ ᗘࢆᐊ ࡲ࡛᪼ ࡋ࡚࠿ࡽ 1.5 ᫬㛫࡯࡝࡛ࠊ⏕ᡂ≀ࡢ

(42)

-39- ⏕ᡂࡀ☜ㄆࡉࢀࡓࠋࡋ࠿ࡋࠊ཯ᛂࢆ⥅⥆ࡉࡏࡓ࡜ࡇࢁᚎࠎ࡟」ᩘࡢ⏕ᡂ≀ࡀ⏕ᡂࡍࡿ⤖ᯝ ࡜࡞ࡾࠊ໬ྜ≀887 ࡢ⏕ᡂࡣ☜ㄆࡍࡿࡇ࡜ࡣฟ᮶࡞࠿ࡗࡓࠋ௨ୖࡼࡾࠊ໬ྜ≀ 87 ࡢㄪ〇ࡣ 㠀ᖖ࡟㞴ࡋࡃࠊ㓄ᗙゎᯒࢆ⾜࠺஦ࡣᅔ㞴ࡔ࡜⪃࠼ࡓࠋ ࡑࡇ࡛ࠊᮏ◊✲࡟࠾࠸࡚ࡣࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫య࡜ྠᵝ࡟୍఩Ⅳ⣲ࡀ sp2 ㌶㐨ࢆ᭷ࡋࠊ༙࢖ࢫᆺ㓄ᗙࢆ࡜ࡿࣛࢡࢺࣥయ 86 ࢆ⏝࠸ࠊ㓄ᗙゎᯒࢆヨࡳࡿࡇ࡜࡜ࡋࡓࠋ o-Xylylene ᆺࣛࢡࢺࣥయ࡜ẚ㍑࡜ࡋ࡚ di-Bn ᆺࣛࢡࢺࣥయࢆ⏝࠸ࠊ㔜ࢪࢡ࣓ࣟࣟࢱࣥ⁐፹ ୰ࠊ-80 ºC ࡟࡚1_{H NMR ࢆ ᐃࡋࡓࠋࡑࡢ⤖ᯝࢆ Table 14 ཬࡧ Fig. 5 ࠿ࡽ Fig. 8 ࡟♧ࡋ}

ࡓࠋ

(43)

-40- Fig. 5 -80 ºC ࡛ࡢo-Xylylene ᆺࣛࢡࢺࣥయࡢ1_{H NMR (4.20 ppm - 3.65 ppm)} Fig. 6 -80 ºC ࡛ࡢo-Xylylene ᆺࣛࢡࢺࣥయࡢ1_{H NMR (8.00 ppm - 3.00 ppm)} H--2 H--3 H--4 H--6, 6’ H--5 H--2 H--3 _H--4 H--6, 6’ H--5

(44)

-41- Fig. 7 -80 ºC ࡛ࡢ di-Bn ᆺࣛࢡࢺࣥయࡢ1_{H NMR (4.35 ppm - 3.60 ppm)} Fig. 8 -80 ºC ࡛ࡢ di-Bn ᆺࣛࢡࢺࣥయࡢ1_{H NMR (8.00 ppm - 3.00 ppm)} H--5 H--2 H--3, H--4 _{H--6, H--6’} H--5 H--2 H--4 H--3 _{H--6, H--6’}

(45)

-42- ᐃࡢ⤖ᯝࡼࡾࠊo-Xylylene ᆺࣛࢡࢺࣥయࡢ 2, 3 ఩ࠊ3, 4 ఩ࠊ4, 5 ఩ࡢ⤖ྜᐃᩘࡀ⣙ 10 Hzࠊ ࡘࡲࡾ஧㠃ゅࡀ⣙180 ᗘ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊo-Xylylene ᆺࣛࢡࢺࣥయ ࡣ-80 ºC ࡟࠾࠸࡚ࡣ4_H₃_{㓄ᗙࡀඃඛⓗ࡟Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ (F}_{Fig. 9)ࠋᚑࡗ࡚ࠊ} ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢ❧య㓄ᗙࡶࣛࢡࢺࣥయ࡜ྠᵝ࡟ 4_H₃_{㓄ᗙࡀඃඛࡋ࡚Ꮡ} ᅾࡋ࡚࠸ࡿࡇ࡜ࡀ᥎ ࡉࢀࡓࠋ Fig. 9 -80 ºC ࡟࠾ࡅࡿo-Xylylene ᆺࣛࢡࢺࣥయࡢ㓄ᗙ ➨஧⠇ ᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸ࡓ⎔≧ಖㆤ⢾౪୚యࡢ㓄ᗙゎᯒ ᭦࡟ࠊᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸࡚࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢ᭱Ᏻᐃ㓄ᗙࢆồ ࡵࡓࠋ࡞࠾ࠊDFT ィ⟬ࡣ GAUSSIAN 0931_{࡟ࡼࡾ⾜࠸ࠊ஺᥮┦㛵ỗ㛵ᩘ࡜ࡋ࡚}_B3LYP32_ࠊ ᇶᗏ㛵ᩘ࡜ࡋ࡚6-311G(d) ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋࡲࡓࠊ⁐፹ຠᯝࡣࠊPolarizable Continuum Model (PCM) ࢆ⏝࠸ࠊࢪࢡ࣓ࣟࣟࢱࣥࢆタᐃࡋࡓࠋ᭦࡟ࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥࡢึ ᮇᵓ㐀ࡣࠊGaussView 533_{ࢆ⏝࠸࡚ᵓ⠏ࡋࡓࠋ} DFT ィ⟬ࡢ⤖ᯝࠊFig 10 ࡟♧ࡋࡓࡼ࠺࡟ࠊ1_{H NMR ࢆ⏝࠸ࡓሙྜ࡜ྠᵝ࡟}4H₃_㓄ᗙࡀ᭱

31_{M. J. Frisch, G. W. Trucks, H. B Schlegel, G. E Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B.}

Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P.Hratchain, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov. T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09, Revision B.01; Gaussian, Inc.: Wallingford CT, 22010.

32_{A. D. Becke,}_{J. Chem. Phys. 11993, 98, 5648-5642.}

(46)

-43- Ᏻᐃ㓄ᗙ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ Fig. 10 ᐦᗘỗ㛵ᩘἲ (DFT) ࡼࡾồࡵࡓ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢ᭱Ᏻᐃ㓄ᗙ ௨ୖࡢ1_{H NMR ཬࡧᐦᗘỗ㛵ᩘἲ (DFT) ࡟ࡼࡿ㓄ᗙゎᯒࡢ⤖ᯝࡼࡾࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ} ࣒࢘࢖࢜ࣥ୰㛫యࡣ-80 ºC࡟࠾࠸࡚4_H₃_{㓄ᗙࡀඃඛⓗ࡟Ꮡᅾࡋࠊ}4_H₃_㓄ᗙࡀ_1,2-_trans_-㑅ᢥ ᛶⓎ⌧࡟኱ࡁࡃᙳ㡪ࢆ୚࠼࡚࠸ࡿ࡜࠸࠺஦ࡀ♧၀ࡉࢀࡓࠋ

(47)

-44- ➨භ❶ 1,2-trans-㑅ᢥᛶⓎ⌧ᶵᵓ࡟㛵ࡍࡿ⪃ᐹ ✀ࠎࡢ᳨ウ⤖ᯝཬࡧ㓄ᗙゎᯒࡢ⤖ᯝࡼࡾࠊᮏ◊✲࡟࠾࠸࡚㛤Ⓨࡋࡓ⎔≧ಖㆤ⢾౪୚యࢆ ⏝࠸ࡓ1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡋࡓᶵᵓ࡟ࡘ࠸࡚௨ୗࡢࡼ࠺࡟⪃ᐹࡋࡓࠋ ࡲࡎࠊࢢࣝࢥ࣮ࢫᆺ౪୚య࡟࠾࠸࡚ࡣࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢ❧య㓄ᗙ࡜ ࡋ࡚⪃࠼ࡽࢀࡿ㓄ᗙࡢ࠺ࡕࠊ2,3 ఩ࡢ⎔≧ಖㆤᇶࡢᏑᅾ࡟ࡼࡾࠊ4H₃_{㓄ᗙࡀඃඛⓗ࡟Ꮡᅾࡋ} ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊཷᐜయ࠿ࡽࡢồ᰾ᨷᧁࡣࠊFelkin-Anh ࣔࢹࣝࡼࡾࠊ࢝ࣝ࣎ࢽ ࣝࡢC=O ࡟ᑐࡋ࡚⣙ 107 º ࡛࠶ࡿ Bürgi-Dunitz ゅࡼࡾ᥋㏆ࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡇࡢ ゅᗘࡣࠊpseudo-equatorial ᪉ྥ࡟㓄ྥࡋࡓ 2 ఩ C-O ⤖ྜ࡜㔜࡞ࡾྜ࠺ࡓࡵࠊ཯Ⓨࡀ⏕ࡌࠊ D㠃ഃ࠿ࡽࡢồ᰾ᨷᧁࡀ㜼ᐖࡉࢀ࡚ࠊE㠃ഃ࠿ࡽࡢồ᰾ᨷᧁ࡟ࡼࡾࠊ1,2-trans-㑅ᢥᛶࡀⓎ⌧ ࡋࡓ࡜⪃࠼ࡓ (FFig. 11)ࠋ࡞࠾ࠊࣉࣟࣆ࢜ࢽࢺࣜࣝ࡜ࢪࢡ࣓ࣟࣟࢱࣥࡢΰྜ⁐፹ࢆ⏝࠸ࡓሙ ྜࡣࠊཷᐜయ࠿ࡽࡢồ᰾ᨷᧁ࡜ྠᵝ࡟ࢽࢺࣜࣝศᏊࡶD㠃ഃ࠿ࡽࡢ㓄఩ࡀ㜼ᐖࡉࢀࠊE㠃ഃ ࡬ࡢ㓄఩ࡀ㉳ࡇࡿࡢ࡛ࠊE㠃ഃ࠿ࡽࡢཷᐜయࡢồ᰾ᨷᧁࡀ㜼ᐖࡉࢀ࡚ 1,2-trans-㑅ᢥᛶࡀప ୗࡋࡓ࡜⪃࠼࡚࠸ࡿࠋࡲࡓࠊTfOH ཬࡧ Tf2NH ࢆ⏝࠸ࡓሙྜࡶྠᵝ࡟ࠊᑐ࢔ࢽ࡛࢜ࣥ࠶ࡿ TfO-_ཬࡧ _Tf₂_N-_{ࡀE㠃ഃࡼࡾồ᰾ᨷᧁࡍࡿࡇ࡜࡛E-ࢺࣜࣇ࣮ࣞࢺཬࡧE-ࢺࣜࣇࣝ࢖࣑ࢻࢆᙧ} ᡂࡋࠊࡇࢀࡽࢆ⤒⏤ࡋ࡚1,2-cis-ࢢࣜࢥࢩࢻࡀ⏕ᡂࡍࡿࠋࡇࡢࡓࡵࠊ୕ࣇࢵ໬࣍࢘⣲ࢪ࢚ࢳ ࢚࣮ࣝࢸࣝ㘒యࢆ⏝࠸ࡓሙྜ࡜ẚ㍑ࡋ࡚ࠊ㑅ᢥᛶࡀపୗࡋࡓ࡜⪃࠼࡚࠸ࡿࠋ Fig. 11 4_H₃_{㓄ᗙ࡟࠾ࡅࡿཷᐜయ࠿ࡽࡢồ᰾ᨷᧁ}

(48)

-45- ୍᪉࡛ࠊ࢞ࣛࢡࢺ࣮ࢫᆺ౪୚యࡢሙྜ (FFig. 12)ࠊ4 ఩ࡢỈ㓟ᇶࡀ axial ᪉ྥ࡟⤖ྜࡋ࡚࠸ ࡿࡓࡵࠊE㠃ഃ࠿ࡽࡢồ᰾ᨷᧁࡀ㜼ᐖࡉࢀ࡚ࠊ1,2-trans-㑅ᢥᛶࡀపୗࡋࡓࡢ࡛ࡣ࡞࠸࠿࡜ ⪃࠼࡚࠸ࡿࠋ Fig. 12 ࢞ࣛࢡࢺ࣮ࢫᆺ౪୚య࡟࠾ࡅࡿཷᐜయ࠿ࡽࡢồ᰾ᨷᧁ ࡞࠾ࠊ4,6 ఩Ỉ㓟ᇶࡢ࡝ࡕࡽ࠿ࠊࡲࡓࡣ୧᪉࡟㟁Ꮚồᘬᇶࢆᑟධࡋࡓ⢾౪୚యࢆ⏝࠸ࡓሙ ྜ࡟㑅ᢥᛶࡢపୗࡀࡳࡽࢀࡓ⌮⏤࡜ࡋ࡚ࡣࠊ4,6 ఩ࡢ㟁Ꮚồᘬᇶ࡟ࡼࡾࠊ⢾⎔ෆࡢ㟁Ꮚ⎔ቃ ࡀኚ໬ࡋࠊ4_H₃_{௨እࡢ㓄ᗙࡀΰᅾࡍࡿࡓࡵ㑅ᢥᛶࡀపୗࡋࡓࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼࡚࠸ࡿࠋ}

(49)

-46- ⥲ᣓ ᮏ◊✲࡟࠾࠸࡚ࠊභ࠿ࡽඵဨ⎔ࢆ᭷ࡍࡿ2,3-⎔≧ಖㆤ౪୚యࢆ⏝࠸ࡿࡇ࡜࡛ࠊ1,2-trans -㑅ᢥⓗ࡟ࢢࣜࢥࢩࢻ໬཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡑࡋ࡚ࠊඵဨ⎔ࢆ᭷ࡍࡿ o-Xylylene ᆺ౪୚యࢆ⏝࠸ࡓヲ⣽࡞᳨ド࡟ࡼࡾࠊ❧య㑅ᢥᛶࡣࠊ1) ཯ᛂ ᗘࠊ2) 4,6 ఩ࡢ Ỉ㓟ᇶಖㆤᇶࠊ3) 4 ఩Ỉ㓟ᇶࡢ㓄ྥ ࡢᙳ㡪ࢆཷࡅࡿࡇ࡜ࡶ᫂ࡽ࠿࡜࡞ࡗࡓࠋ᭦࡟ࠊ௒ᚋࡢ ⢾㙐ྜᡂ࡬ࡢᛂ⏝ࢆど㔝࡟ධࢀࠊ㧗࠸1,2-trans-㑅ᢥᛶࢆ♧ࡋࠊ㓟ᛶ᮲௳ୗ࡟࡚㑅ᢥⓗ࡞⎔ ≧ಖㆤᇶࡢ㝖ཤࡀྍ⬟࡛࠶ࡿ2,3-ࢼࣇࢱࣞࣥࢪ࣓ࢳࣝᆺ౪୚యࡢ㛤Ⓨ࡟ࡶᡂຌࡋࡓࠋ ࡲࡓࠊ1_{H NMR ཬࡧᐦᗘỗ㛵ᩘἲ (DFT) ࢆ⏝࠸࡚࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡢࣔ} ࢹࣝ໬ྜ≀ࡢ㓄ᗙゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊࣔࢹࣝ໬ྜ≀ࡣ-80 ºC ࡟࠾࠸࡚4H₃_{㓄ᗙࡀඃඛⓗ} ࡟Ꮡᅾࡍࡿࡇ࡜ࡀࢃ࠿ࡾࠊ࢜࢟ࢯ࢝ࣝ࣋ࢽ࣒࢘࢖࢜ࣥ୰㛫యࡶྠᵝ࡟ 4_H₃_{㓄ᗙࢆ⤒⏤ࡋ࡚} 1,2-trans-㑅ᢥᛶࡀⓎ⌧ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ ᮏ◊✲࡛㛤Ⓨࡋࡓ᪉ἲࡣࠊ᭱ࡶỗ⏝ࡉࢀ࡚࠸ࡿ⬺㞳ᇶ࡜άᛶ໬๣ࢆ⏝࠸࡚⾜࠺஦ࡀྍ⬟ ࡞ࠊ㞄᥋ᇶຠᯝ࡟౫ࡽ࡞࠸᪂ࡓ࡞1,2-trans-㑅ᢥⓗࢢࣜࢥࢩࣝ໬࡛࠶ࡿࠋࡇࡢ᪉ἲࢆ⏝࠸ࡿ ࡇ࡜࡛ࠊศᏊෆ࡟࢚ࢫࢸࣝ⤖ྜࢆ᭷ࡍࡿศᏊࡢྜᡂ࡟᭷⏝࡛࠶ࡿࡇ࡜ࡀᮇᚅ࡛ࡁࡿࠋ

(50)

-47-

ᐇ

ᐇ㦂ࡢ㒊

୍⯡᧯స

཯ᛂ⁐፹ (CH2Cl2, toluene, THF, CH3CN, DMF, pyridine) ࡣ Kanto Chemical Co. Inc.

࡟࡚㉎ධࡋࡓࡶࡢࢆ⏝࠸ࡓࠋ࣮ࣔࣞ࢟ࣗࣛࢩ࣮ࣈࢫࡣWako Chemicals Inc. ࡢࡶࡢࢆ 300 |C ࡟࡚ 2 ᫬㛫άᛶ໬ࡉࡏ࡚࠿ࡽ⏝࠸ࡓࠋTLC ศᯒ࡟ࡣ Merck TLC (Silica Gel 60F254 on

glass plate) ࢆ⏝࠸ࠊ໬ྜ≀ࡢ᳨ฟ࡟ࡣ UV ྾཰ (254 nm)ࠊཬࡧⓎⰍヨ⸆ (10 % H2SO4 in

EtOH, phosphomolybdic acid solution 5 wt.% in EtOH, phosphomolybdic acid solution 20 wt.% in EtOH) ࢆ⏝࠸ࡓࠋࣇࣛࢵࢩࣗࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ࡣ Fuji Silysia Co. 〇ࡢ Silica gel (80 mesh, 300 mesh) ࢆ⏝࠸ࠊヨᩱࡢ 100-200 ಸ㔜㔞ࢆ඘ሸࡋ ࡓࠋࢤࣝℐ㐣ࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ࡣSephadex (Pharmacia LH-20) ࢆ⏝࠸ࡓࠋ⏝࠸ࡓ⁐ ฟ⁐፹ࡣయ✚ẚ࡛ ( ) ࡟♧ࡋࡓࠋࡍ࡭࡚ࡢ⃰⦰᧯సࡣࠊ‮ᾎ࡟ࡼࡿຍ ࡜ῶᅽ᮲௳ୗ࡛⾜ࡗ ࡓࠋ1_{H NMRࠊ}13_{C NMR ࢫ࣌ࢡࢺࣝࡣ Bruker (500 MHz) ࢆ⏝࠸࡚ ᐃࡋࠊࢣ࣑࢝ࣝࢩࣇ}

ࢺ್ࡣෆ㒊ᶆ‽≀㉁ (Tetramethylsilane) ࡟ᑐࡍࡿδ್ (ppm) ࡛♧ࡋࡓࠋࢫ࣌ࢡࢺࣝࢹ࣮ ࢱ࡟ࡣࢩࢢࢼࣝࡢᙧ≧࡟ࡼࡾḟࡢࡼ࠺࡟グࡋࡓ (ซ౛㸸s = singlet, d = doublet, t = triplet, q = quartet, dd = double doublet, td = triple doublet, m = multiplet and/or multiple resonances)ࠋ㉁㔞ศᯒࡣ Bruker micrOTOF (ESI-TOF MS) ࢆ⏝࠸࡚ positive-ion ࣮ࣔࢻ ࡛ ᐃࡋࡓࠋẚ᪕ගᗘࡣHoliba SEPA-300 㧗ឤᗘ᪕ගගᗘィࢆ⏝࠸࡚ ᐃࡋࡓࠋ ᐃ࡟౑ ⏝ࡋࡓ⁐፹࡜⃰ᗘࡣ ( ) ෆ࡟♧ࡋࡓࠋ

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Phenyl 4,6-O-bbenzylidene-2,3-O-((1,1,3,3-tetraisopropyldisiloxanylidene)-1-thio -E-D-glucopyranoside (7)

Ar 㞺ᅖẼୗ࡟࡚ࠊ໬ྜ≀ 4 (3.00 g, 8.30 mmol) ࢆ DMF (83.0 㹫L) ࡟⁐࠿ࡋࠊ 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (7.70 mL, 25.0 mmol) ཬࡧ imidazole (3.40 g, 50.0 mmol) ࢆᐊ ࡟࡚ຍ࠼ࡓᚋࠊ50 |C ࡟᪼ ࡋࠊ30 ศ᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊịᾎ࡟࡚㣬࿴Ⅳ㓟Ỉ⣲ࢼࢺ࣒ࣜ࢘ࢆຍ࠼཯ᛂࢆ೵Ṇࡋ ࡓᚋࠊEtOAc ࡛ᢳฟࡋࠊὙί (Ỉࠊ㣬࿴㣗ሷỈ)ࠊ஝⇱ (↓Ỉ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ ⁐፹␃ཤᚋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (EtOAc/n-Hexane = 1/15) ࡛⢭ 〇ࡋࠊ໬ྜ≀7 (5.00 g, quant.) ࢆ↓Ⰽ⢓ᛶᾮయ࡜ࡋ࡚ᚓࡓࠋ[D]D -16.0 ° (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.58-7.18 (m, 10 H, 2 Ph), 5.57 (s, 1 H, >CHPh), 4.71 (d, 1 H,

J1,2 = 9.5 Hz, H-1), 4.36 (dd, 1 H, J5,6a = 5.0 Hz, Jgem = 10.5 Hz, H-6a), 3.89 (t, 1 H, J2,3 =

J3,4 = 9.5 Hz, H-3), 3.79 (t, 1 H, J5,6b = 10.5 Hz, H-6b), 3.72 (t, 1 H, H-2), 3.59 (t, 1 H, J4,5

= 9.5 Hz, H-4), 3.44 (td, 1 H, H-5), 1.18-0.86 (m, 28 H, 4 i_Pr);13_{C NMR (125 MHz, CDCl}₃₎

δ 137.5, 134.2, 131.7, 128.9, 128.7, 128.1, 128.1, 127.5, 125.9, 101.0, 89.8, 80.3, 77.8, 76.5, 70.6, 68.7, 17.5, 17.4, 17.2, 17.2, 17.2, 17.1, 17.0, 12.9, 12.8, 12.3; HRMS (ESI) m/z: found [M+Na]+_{625.2244, C}₃₁_H₄₆_O₆_SSi₂_{calcd for [M+Na]}+_625.2246.

Phenyl 4-O-bbenzyl-2,3-O-((1,1,3,3-tetraisopropyldisiloxanylidene)-1-thio -E-D-glucopyranoside (8)

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Ar 㞺ᅖẼୗ࡟࡚ࠊάᛶ໬ࡋࡓ molecular sieves 4Å (1.00 g) ࡟ࠊ໬ྜ≀ 77 (1.00 g, 1.70 mmol) ࡢ CH2Cl2 (16.0 mL) ⁐ᾮࢆᐊ ࡟࡚ຍ࠼࡚ 30 ศ㛫᧠ᢾࡋࡓࠋ-80|C ࡟෭༷ࡋࠊ

dichlorophenylborane (650 μL, 4.40 mmol) ཬࡧ triethylsilane (680 μL, 4.40 mmol) ࢆຍ ࠼ࠊ5.5 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊEt3N ཬࡧ

MeOH ࢆຍ࠼཯ᛂࢆ೵ṆࡋࡓᚋࠊCHCl3࡛ᕼ㔘ࡋࡓࠋ⁐ᾮࢆࢭࣛ࢖ࢺℐ㐣ࡋࠊᚓࡽࢀࡓℐ

ᾮ࡜Ὑᾮࢆྜࢃࡏ࡚Ὑί (㣬࿴Ⅳ㓟Ỉ⣲ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮࠊỈࠊ㣬࿴㣗ሷỈ)ࠊ஝⇱ (↓Ỉ ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ⁐፹␃ཤᚋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (EtOAc/n-Hexane = 1/7) ࡛⢭〇ࡋࠊ໬ྜ≀ 8 (1.00 g, quant.) ࢆⓑⰍᅛయ࡜ࡋ࡚ᚓࡓࠋ[D]D

-11.5 ° (c 0.7, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.47-7.23 (m, 10 H, 2 Ph), 4.95 (d, 1

H, Jgem = 11.5 Hz, PhCH2), 4.65 (d, 1 H, J1,2 = 9.5 Hz, H-1), 4.64 (d, 1 H, PhCH2), 3.87 (t,

1 H, J2,3 = J3,4 = 8.5 Hz, H-3), 3.80 (td, 1 H, J5,6a = 3.0 Hz, J6a,OH = 7.0 Hz, Jgem = 10.0 Hz,

H-6a), 3.66 (dd, 1 H, H-2), 3.61 (m, 1 H, H-6b), 3.49 (t, 1 H, J4,5 = 8.5 Hz, H-4), 3.37-3.33

(m, 1 H, H-5), 1.78 (t, 1 H, J6b,OH = 7.0 Hz, OH), 1.17-0.97 (m, 28 H, 4 iPr); 13C NMR (125

MHz, CDCl3) δ 138.0, 134.3, 131.4, 128.9, 128.5, 128.3, 127.9, 127.3, 88.4, 82.2, 78.9,

77.7, 75.8, 75.4, 62.4, 17.6, 17.5, 17.5, 17.5, 17.3, 17.2, 17.2, 12.9, 12.8, 12.3; HRMS (ESI) m/z: found [M+Na]+ _{672.2602, C}₃₂_H₄₈_O₇_SSi₂_{calcd for [M+Na]}+_672.2602.

Phenyl 4,6-di-O-bbenzyl-2,3-O-((1,1,3,3-tetraisopropyldisiloxanylidene)-1-thio -E-D-glucopyranoside (9)

Ar 㞺ᅖẼୗ࡟࡚ࠊ໬ྜ≀ 8 (350 mg, 579 μmol) ࢆ DMF (2.90 mL) ࡟⁐࠿ࡋࠊbenzyl bromide (344 μL, 2.90 mmol) ཬࡧ sodium hydride (60.4 mg, 868 μmol) ࢆ-20|C ࡟࡚ຍ

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࠼ࠊ4.0 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊMeOH ࢆຍ ࠼཯ᛂࢆ೵Ṇࡋࡓᚋࠊࢺ࢚ࣝࣥඹἛࢆ⾜࠸ࠊṧ´ࢆEtOAc ࡛ᢳฟࡋࠊὙί (Ỉࠊ㣬࿴㣗ሷ Ỉ)ࠊ஝⇱ (↓Ỉ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ⁐፹␃ཤᚋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟ ࢺࢢࣛࣇ࢕࣮ (EtOAc/n-Hexane = 1/30) ࡛⢭〇ࡋࠊ໬ྜ≀ 99 (320 mg, 79%) ࢆⓑⰍᅛయ࡜ ࡋ࡚ᚓࡓࠋ[D]D -16.5 ° (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.68-7.18 (m, 15 H, 3 Ph), 4.93 (d, 1 H, Jgem = 11.0 Hz, PhCH2), 4.61 (d, 1 H, J1,2 = 9.5 Hz, H-1), 4.57 (d, 1 H, PhCH2), 4.59 (d, 1 H, Jgem = 12.5 Hz, PhCH2), 4.50 (d, 1 H, PhCH2), 3.84 (t, 1 H, J2,3 = J3,4 = 9.0 Hz, H-3), 3.74-3.69 (m, 2 H, H-2, H-5), 3.64 (dd, 1 H, J5,6a = 4.5 Hz, Jgem = 10.5 Hz, H-6a), 3.54 (t, 1 H, J4,5 = 9.0 Hz, H-4), 3.47 (dd, 1 H, J5,6b = 5.0 Hz, H-6b), 1.15-0.98 (m, 28 H, 4 i_Pr);13_{C NMR (125 MHz, CDCl}₃_{) δ 138.3, 138.2, 134.9, 131.3, 128.8, 128.3, 128.1,} 127.7, 127.7, 127.5, 127.0, 88.5, 82.3, 80.0, 78.8, 77.6, 75.7, 75.4, 73.4, 69.2, 30.9, 17.6, 17.5, 17.5, 17.3, 17.3, 17.3, 17.2, 12.9, 12.8, 12.3, 12.3; HRMS (ESI) m/z: found [M+Na]+

717.3075, C32H48O7SSi2 calcd for [M+Na]+ 717.3072.

Phenyl 4,6-O-bbenzylidene-1-thio-2,3-O-((o-xylylene)-E-D-glucopyranoside (10) Ar 㞺ᅖẼୗ࡟࡚ࠊ໬ྜ≀ 4 (5.00 g, 12.8 mmol) ࢆ DMF (256 mL) ࡟⁐࠿ࡋࠊsodium hydride (2.60 g, 64.0 mmol) ࢆ ị ᾎ ࡟ ࡚ ຍ ࠼ ࠊ 30 ศ ᧠ ᢾ ࡋ ࡓ ࠋ ࡑ ࡢ ᚋ ࠊ D-D’-dibromo-o-xylene (3.80 g, 14.1 mmol) ࢆຍ࠼ࠊᐊ ࡟࡚ 11.5 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊ ஢ࢆTLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊịᾎ࡟࡚ MeOH ࢆຍ࠼཯ᛂࢆ೵Ṇࡋࡓᚋࠊ EtOAc ࡛ᢳฟࡋࠊὙί (Ỉࠊ㣬࿴㣗ሷỈ)ࠊ஝⇱ (↓Ỉ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ⁐፹␃ ཤᚋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (CHCl3/Toluene = 1/1) ࡛⢭〇ࡋࠊ໬

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ྜ≀110 (5.00 g, 84%) ࢆ㯤Ⰽᅛయ࡜ࡋ࡚ᚓࡓࠋ[D]D +6.5 ° (c 1.0, CHCl3); 1H NMR (500

MHz, CDCl3) δ 7.55-7.12 (m, 14 H, 3 Ar), 5.51 (s, 1 H, >CHPh), 5.18 (d, 1 H, Jgem = 13.5

Hz, ArCH2), 5.15 (d, 1 H, Jgem = 9.5 Hz, ArCH2), 5.12 (d, 1 H, ArCH2), 4.89 (d, 1 H,

ArCH2), 4.71 (d, 1 H, J1,2 = 9.5 Hz, H-1), 4.34 (dd, 1 H, J5,6a = 4.5 Hz, Jgem = 10.5 Hz,

H-6a), 3.82 (t, 1 H, J2,3 = J3,4 = 9.0 Hz, H-3), 3.73 (t, 1 H, J5,6b = 10.5 Hz, H-6b), 3.53 (t, 1

H, J4,5 = 9.0 Hz, H-4), 3.50-3.46 (m, 2 H, H-2, H-5); 13C NMR (125 MHz, CDCl3) δ 139.0,

137.1, 136.6, 136.4, 132.9, 132.3, 131.3, 129.1, 129.1, 129.0, 128.3, 128.1, 127.9, 127.2, 126.4, 120.9, 101.8, 87.7, 81.4, 79.4, 79.3, 79.3, 73.5, 73.0, 72.4, 70.3, 68.6; HRMS (ESI) m/z: found [M+Na]+_{485.1391, C}₂₇_H₂₆_O₅_{S calcd for [M+Na]}+_485.1393.

Phenyl 4-O-bbenzyl-1-thio-2,3-O-((o-xylylene)-E-D-glucopyranoside (11)

Ar 㞺ᅖẼୗ࡟࡚ࠊάᛶ໬ࡋࡓ molecular sieves 4Å (350 mg) ࡟ࠊ໬ྜ≀ 10 (1.00 g, 1.70 mmol) ࡢ CH2Cl2 (7.20 mL) ⁐ᾮࢆᐊ ࡟࡚ຍ࠼࡚ 30 ศ㛫᧠ᢾࡋࡓࠋ-80 |C ࡟෭༷ࡋࠊ

dichlorophenylborane (334 μL, 2.58 mmol) ཬࡧ triethylsilane (265 μL, 2.58 mmol) ࢆຍ ࠼ࠊ1.0 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊEt3N ཬࡧ

MeOH ࢆຍ࠼཯ᛂࢆ೵ṆࡋࡓᚋࠊCHCl3࡛ᕼ㔘ࡋࡓࠋ⁐ᾮࢆࢭࣛ࢖ࢺℐ㐣ࡋࠊᚓࡽࢀࡓℐ

ᾮ࡜Ὑᾮࢆྜࢃࡏ࡚Ὑί (㣬࿴Ⅳ㓟Ỉ⣲ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮࠊỈࠊ㣬࿴㣗ሷỈ)ࠊ஝⇱ (↓Ỉ ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ⁐፹␃ཤᚋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (EtOAc/n-Hexane = 1/7) ࡛⢭〇ࡋࠊ໬ྜ≀ 11 (323 mg, 92%) ࢆⓑⰍᅛయ࡜ࡋ࡚ᚓࡓࠋ[D]D

+50.3 ° (c 2.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.37-7.12 (m, 14 H, 3 Ar), 5.18 (d, 1

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11.0 Hz, ArCH2), 4.85 (d, 1 H, ArCH2), 4.66 (d, 1 H, ArCH2), 4.63 (d, 1 H, J1,2 = 9.5 Hz,

H-1), 3.83 (m, 1 H, H-6a), 3.72 (t, 1 H, J2,3 = J3,4 = 8.5 Hz, H-3), 3.62 (m, 1 H, H-6b), 3.45

(t, 1 H, J4,5 = 8.5 Hz, H-4), 3.37-3.36 (m, 2 H, H-2, H-5), 1.84 (t, 1 H, J6a,OH = J6b,OH = 5.0

Hz, OH); 13_{C NMR (125 MHz, CDCl}₃_{) δ 138.3, 136.8, 136.6, 133.1, 131.9, 130.7, 129.3,}

129.0, 128.5, 128.3, 128.2, 128.1, 128.0, 127.9, 127.7, 86.6, 86.0, 79.6, 79.0, 76.7, 75.0, 73.1, 73.0, 62.4; HRMS (ESI) m/z: found [M+Na]+_{487.1554, C}₃₄_H₃₄_O₅_{S calcd for}

[M+Na]+_487.1550.

Phenyl 4,6-di-O-bbenzyl-1-thio-2,3-O-((o-xylylene)-E-D-glucopyranoside (12)

Ar 㞺ᅖẼୗ࡟࡚ࠊ໬ྜ≀ 11 (331 mg, 713 μmol) ࢆ DMF (3.60 mL) ࡟⁐࠿ࡋࠊsodium hydride (42.8 mg, 1.07 mmol) ࢆ-20 |C ࡟࡚ຍ࠼ࠊ30 ศ᧠ᢾࡋࡓࠋࡑࡢᚋࠊbenzyl bromide (423 μL, 3.56 mmol) ࢆຍ࠼ࠊ2.0 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/n-Hexane = 1/3) ࡛☜ㄆᚋࠊMeOH ࢆຍ࠼཯ᛂࢆ೵Ṇࡋࡓᚋࠊࢺ࢚ࣝࣥඹἛࢆ⾜࠸ࠊṧ´ࢆ EtOAc ࡛ᢳฟࡋࠊ Ὑί (Ỉࠊ㣬࿴㣗ሷỈ)ࠊ஝⇱ (↓Ỉ◲㓟ࢼࢺ࣒ࣜ࢘) ࢆ⾜ࡗࡓࠋ⁐፹␃ཤᚋࠊṧ´ࢆࢩࣜ ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (EtOAc/Toluene = 1/10) ࡛⢭〇ࡋࠊ໬ྜ≀ 12 (395 mg, quant.) ࢆⓑⰍᅛయ࡜ࡋ࡚ᚓࡓࠋ[D]D +22.1 ° (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ

7.73-7.11 (m, 19 H, 3 Ar), 5.17 (d, 1 H, Jgem = 13.5 Hz, ArCH2), 5.09 (s, 2 H, 2 ArCH2),

4.92 (d, 1 H, Jgem = 11.0 Hz, ArCH2), 4.90 (d, 1 H, ArCH2), 4.59 (d, 1 H, J1,2 = 10.0 Hz,

H-1), 4.56 (d, 2 H, Jgem = 15.5 Hz, 2 ArCH2), 4.50 (d, 1 H, ArCH2), 3.76 (d, 1 H, Jgem =

10.5 Hz, H-6a), 3.70 (t, 1 H, J 2,3 = J 3,4 = 8.5 Hz, H-3), 3.66 (dd, 1 H, J5,6b = 4.5 Hz, H-6b),

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CDCl3) δ 138.3, 138.2, 134.9, 131.3, 128.8, 128.3, 128.1, 127.7, 127.7, 127.5, 127.0, 88.5,

82.3, 78.8, 77.9, 75.6, 75.4, 73.4, 69.2, 30.9, 17.6, 17.5, 17.5, 17.3, 17.3, 17.2, 17.2, 12.9, 12.8, 12.3, 12.3; HRMS (ESI) m/z: found [M+Na]+_{577.2016, C}₃₄_H₃₄_O₅_{S calcd for}

[M+Na]+_577.2019.

Phenyl 44,6-di-O-bbenzyl-2,3-O-((2’,3’-dimethoxybutane-2’,3’-diyl)-E -D-glucopyranoside (15)

Ar 㞺ᅖẼୗ࡟࡚ࠊ໬ྜ≀ 14 (53.7 mg, 119 μmol) ࢆ MeOH (600 μL) ࡟⁐࠿ࡋࠊ butane-2,3-dione (79.0 μL, 890 μmol)ࠊBF3∙OEt2 (12.7 μL, 11.9 μmol) ཬࡧ trimethyl

orthoformate (104 μL, 950 μmol) ࢆᐊ ࡟࡚ຍ࠼ࠊ42 ᫬㛫᧠ᢾࡋࡓࠋ཯ᛂ⤊஢ࢆ TLC (EtOAc/Toluene = 1/10) ࡛☜ㄆᚋࠊ཯ᛂᾮࢆ⃰⦰ࡋࠊṧ´ࢆࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢ ࣛࣇ࢕࣮ (EtOAc/n-Hexane = 1/10 Ѝ 1/3) ࡛⢭〇ࡋࠊ໬ྜ≀ 15 (64.4 mg, 84%) ࢆ↓Ⰽ⢓ ᛶᾮయ࡜ࡋ࡚ᚓࡓࠋ[D]D -92.2 ° (c 0.9, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.56-7.19 (m, 15 H, 3 Ph), 4.92 (d, 1 H, Jgem = 11.0 Hz, PhCH2), 4.74 (d, 1 H, J1,2 = 9.5 Hz, H-1), 4.58 (d, 1 H, Jgem = 12.0 Hz, PhCH2), 4.57 (d, 1 H, PhCH2), 4.51 (d, 1 H, PhCH2), 3.92 (t, 1 H, J2,3 = J3,4 = 9.5 Hz, H-3), 3.78-3.68 (m, 4 H, H-2, H-4, H-6a, H-6b), 3.53 (m, 1 H, H-5), 3.29 (s, 3 H, OCH3), 3.20 (s, 3 H, OCH3), 1.35-1.34 (2 s, 6 H, 2 CH3); 13C NMR (125 MHz, CDCl3) δ 138.4, 138.3, 133.5, 131.6, 128.7, 128.3, 128.3, 128.0, 127.7, 127.6, 127.5, 127.2, 100.1, 99.5, 84.8, 79.5, 77.6, 75.5, 75.0, 74.6, 73.4, 69.1, 68.0, 48.1, 47.9, 17.8, 17.6; HRMS (ESI) m/z: found [M+Na]+_{589.2230, C}₃₁_H₃₈_O₇_{S calcd for [M+Na]}+_589.2230.