上原記念生命科学財団研究報告集, 34 (2020)ୖཎグᛕ⏕࿨⛉Ꮫ㈈ᅋ◊✲ሗ࿌㞟, 34㸦2020㸧

121. ࣓ࢱ࣮ࣞࢺ㌿఩ࢆά⏝ࡍࡿ୕ḟඖ᭷ᶵ࣎ࣟࣥ㓟ࡢᵓ⠏⁁ཱྀ ⋞ᶞᒸᒣ኱Ꮫ ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉ ᛂ⏝໬ᏛᑓᨷKey words㸸᭷ᶵ࣍࢘⣲໬ྜ≀㸪1,2-࣓ࢱ࣮ࣞࢺ㌿఩㸪࣍࢘⣲࢔࣮ࢺ㘒య㸪࣎ࣛࢧ࢖ࢡࣝ㸪ࢩࢡࣟࣉࣟࣃࣥ⥴ ゝ᭷ᶵ࣍࢘⣲໬ྜ≀ࡣኳ↛≀ࡸ་⸆ရࠊᶵ⬟ᛶศᏊ࡞࡝ࡢྜᡂ࡟࠾ࡅࡿࣅࣝࢹ࢕ࣥࢢࣈࣟࢵࢡ࡜ࡋ࡚ᴟࡵ࡚㔜せ࡞୍⩌࡛࠶ࡿࠋࡲࡓࠊᢠࡀࢇ๣࣎ࣝࢸࢰ࣑ࣈ࡟௦⾲ࡉࢀࡿࡼ࠺࡟ࠊྵ࣍࢘⣲་⸆ရࡣ࣍࢘⣲ඖ⣲ࡀᣢࡘ≉ᛶ㸦✵ࡢ㌶㐨࡟ࡼࡿࣝ࢖ࢫ㓟ᛶ࣭࣎ࣟࣥ㓟ᵓ㐀࡟ࡼࡿỈ⣲⤖ྜᙧᡂࡸ࢚ࢫࢸࣝᙧᡂ㸧࡟ࡼࡾ≉␗࡞⏕⌮άᛶࢆ♧ࡍࠋࡑࡢࡓࡵࠊᵓ㐀ࡢ」㞧
࡞࢔ࣝ࢟ࣝ࣍࢘⣲ࢆ❧య㑅ᢥⓗ࡟ᵓ⠏࡛ࡁࡿ᪂ࡋ࠸ྜᡂᡓ␎ࡢ㛤Ⓨ࡟⯆࿡ࡀᣢࡓࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ࣍࢘⣲࡜࠸࠺ඖ⣲ࡢ≉ᛶࢆ⏕࠿ࡍࡇ࡜࡛ࠊࢩࣥࣉࣝ࡞ࣅࣝࢹ࢕ࣥࢢ࠿ࡽࠊศᏊ㦵᱁ࢆ❧య㑅ᢥⓗ࡟⤌ࡳୖࡆ࡞ࡀࡽ࣍࢘⣲ࣘࢽࢵࢺࢆ
ᑟධ࡛ࡁࡿ┤ᡖⓗ࡞ࣉࣟࢭࢫࡢ㛤Ⓨࢆ┠ⓗ࡜ࡋࠊ࢔ࣝࢣࢽࣝ࣍࢘⣲࢔࣮ࢺ㘒యࡢ 1,2–࣓ࢱ࣮ࣞࢺ㌿఩㹙1㹛࡟╔┠ࡋࡓࠋ࢔ࣝࢣࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢ≉ᛶ࡜ࡋ࡚ࠊồ㟁Ꮚ๣ࢆࢺ࣮ࣜ࢞࡜ࡍࡿ 1,2–࣓ࢱ࣮ࣞࢺ㌿఩ࡀ▱ࡽࢀ࡚࠸ࡿ㸦ᅗ 1a㸧ࠋồ㟁Ꮚ๣࡟ࡼࡾ࢜ࣞࣇ࢕ࣥࢆάᛶ໬ࡍࡿࡇ࡜࡛࣍࢘⣲ୖࡢ⨨᥮ᇶࡀồ㟁Ꮚ๣ࡢ࢔ࣥࢳഃ࠿ࡽ㌿఩ࡋࠊ  Ⅳ⣲̿Ⅳ⣲⤖ྜࢆᙧᡂࡍࡿ཯ᛂ࡛࠶ࡾࠊ࢜ࣞࣇ࢕ࣥࢆ 1,2–ᐁ⬟ᇶ໬ࡋ࡞ࡀࡽከ⨨᥮࣎ࣟࣥ㓟ㄏᑟయࢆྜᡂࡍࡿᡭἲ࡛
࠶ࡿࠋ㏆ᖺࠊMorken ࡽࡸ Aggarwal ࡽࢆ୰ᚰ࡜ࡋ࡚ࡇࡢࡼ࠺࡞཯ᛂᛶࢆά⏝ࡍࡿᡭἲࡀ㛤Ⓨࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚  ࡁࡓࡀࠊ᪤Ꮡࡢᡭἲࡣࢩࣥࣉࣝ࡞ᇶ㉁ࡢ࢝ࢵࣉࣜࣥࢢࡀ୰ᚰ࡛࠶ࡾ㹙2㸪3㹛
ࠊ࣓ࢱ࣮ࣞࢺ㌿఩ࢆά⏝ࡋ࡚⎔ᵓ㐀ࡢࡼ࠺࡞୕ḟඖⓗ࡞ᵓ㐀ࢆ❧యไᚚࡋ࡞ࡀࡽྜᡂࡍࡿᡓ␎ࡣᮍ㛤ᣅ࡛࠶ࡿ㸦ࡈࡃ᭱㏆ Aggarawal ࡽ࡟ࡼࡾ⎔⦰ᑠࡸᣑ኱ࢆ⤒ࡿ࣓ࢱ࣮ࣞࢺ㌿఩ࡀሗ࿌ࡉࢀࡓ㹙4㸪5㹛㸧ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ࣎ࣛࢧ࢖ࢡࣝࡢ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࠊ࠾ࡼࡧ   ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟ࡢṍࡳ㛤ᨺᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࠊࢆ࣮࣮࢟࣡ࢻ࡜ࡋ࡚ࠊ⎔ᵓ㐀ࢆᣢࡘከ⨨᥮࣍࢘⣲໬ྜ≀ࢆຠ⋡ⓗ࡟ྜᡂྍ⬟࡞ᡓ␎ࢆ㛤Ⓨࡍࡿࡇ࡜┠ᣦࡋࡓࠋ௒ᅇࠊศᏊෆ࡟ࢩ࢔ࣀᇶࢆᣢࡘࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩㸦ᅗ 1b㸧ࡢ᳨ウࢆ⾜࠸ࠊึᮇⓗ࡞ẁ㝵࡞ࡀࡽ㌿఩⏕ᡂ≀ࢆᚓࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡲࡓࠊࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢㄪ〇࡜ࡑࡢ཯ᛂᛶࢆㄪᰝࡋࠊ
࢝ࢵࣉࣜࣥࢢ཯ᛂࢆ㛤Ⓨࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ 1c㸧ࡓࡵ௨ୗ࡟ሗ࿌ࡍࡿࠋ

ᅗ 1㸬࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢ 1,2㸫࣓ࢱ࣮ࣞࢺ㌿఩a㸧 ࣓ࢱ࣮ࣞࢺ㌿఩ࡢ୍⯡ᘧࠋb㸧 ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩࡟ࡼࡿከᐁ⬟ᛶࢩࢡࣟ࢔ࣝ࢟ࣝ࣎ࣟࣥ㓟ࡢྜᡂࠋc㸧 ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢṍࡳ㛤ᨺᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࠋ1ୖཎグᛕ⏕࿨⛉Ꮫ㈈ᅋ◊✲ሗ࿌㞟, 34㸦2020㸧㻌᪉ ἲ1㸬 ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩࡟ࡼࡿከ⨨᥮ࢩࢡࣟ࢔ࣝ࢟ࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢྜᡂィ⏬
⎔⦰ᑠᆺࡢ࣓ࢱ࣮ࣞࢺ㌿఩ࢆᐇ⌧ࡍࡿࡓࡵࠊᇶ㉁࡜ࡋ࡚ࢩ࢔ࣀᇶࢆᣢࡘࣅࢽࣝ࣎ࣟࣥ㓟ࢆタィࡋࠊሷᇶᛶ᮲௳ୗ࡛Ⓨ⏕ࡉࡏࡓࢩ࢔ࣀ࢝ࣝࣂࢽ࢜ࣥࡢ࣍࢘⣲࡬ࡢ⎔໬཯ᛂ࡟ࡼࡾ࣎ࣛࢧ࢖ࢡࣝࢆᵓ⠏ࡍࡿࡇ࡜࡜ࡋࡓࠋࡇࡇ࡟ồ㟁Ꮚ๣ࢆస⏝ࡉࡏࡿࡇ࡜࡛࣓ࢱ࣮ࣞࢺ㌿఩ࢆᘬࡁ㉳ࡇࡋࢩࢡࣟ࣌ࣥࢳࣝ࣎ࣟࣥ㓟ࢆྜᡂࡍࡿࠋࡇࡢ㝿ࠊ୰㛫య࡜࡞ࡿ࢔࣮ࢺ㘒యࡢᏳᐃ໬࠾ࡼࡧ㌿఩ࡢ❧యไᚚࢆ┠ⓗ࡜ࡋࠊᇶ㉁࡟ᑟධࡋࡓỈ㓟ᇶࢆ࣍࢘⣲ཎᏊ࡟㓄఩ࡉࡏࡿ཯ᛂไᚚἲࢆ⪃᱌ࡋࡓ㸦ᅗ 2㸧ࠋỈ㓟ᇶࡢ㓄఩࡟ࡼࡾࣅࢩࢡࣟᆺࡢ࣎ࣛࢧ࢖ࢡࣝࢆᙧᡂࡍࡿࡓࡵࠊ㌿఩ࢆ❧య㑅ᢥⓗ࡟⾜࠺ࡇ࡜ࡀ࡛ࡁࡿ࡜ ᮇᚅࡋࡓࠋ

ᅗ 2㸬࢔ࣝࢥ࢟ࢩࢻࢆ㓄ྥᇶ࡜ࡍࡿ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࢩ࢔ࣀᇶࢆᣢࡘࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆሷᇶᛶ᮲௳ୗ⎔໬ࡉࡏࠊ⏕ࡌࡓ࣎ࣛࢧ࢖ࢡࣝ࡟ồ㟁Ꮚ๣ࢆస⏝ࡉࡏࡇ࡜࡛⎔⦰ᑠࢆక࠺㌿఩ࡀ㐍⾜ࡍࡿ࡜ᮇᚅࡋࡓࠋ2㸬ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢṍࡳ㛤ᨺᆺ࣓ࢱ࣮ࣞࢺ㌿఩཯ᛂࡢ㛤Ⓨࢩࢡࣟ࢔ࣝࢣࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࢆồ㟁Ꮚ๣࡛άᛶ໬ࡍࢀࡤࠊ࣓ࢱ࣮ࣞࢺ㌿఩࡟ࡼࡗ࡚ᐁ⬟ᇶ໬ࡉࢀࡓ⎔≧࣎ࣟࣥ㓟࢚ࢫࢸࣝࡀ❧య≉␗ⓗ࡟ྜᡂ࡛ࡁࡿࠋࣚ࢘⣲໬๣ࢆồ㟁Ꮚ๣࡜ࡍࡿࡇ࡜࡛࣓ࢱ࣮ࣞࢺ㌿఩ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊ㏻ᖖࡍࡄ࡟࣍࢘⣲࡜ࣚ࢘⣲ࡀ⬺㞳ࡋ࢔ࣝࢣࣥࢆ୚࠼ࡿ㸦Zweifel ࢜ࣞࣇ࢕ࣥ໬㹙6㹛㸧ࠋࡇࡇ࡛ࡣ  ࣚ࢘⣲࡜࣍࢘⣲ࠊࡑࡋ࡚ࡑࢀࡽࡢ❧య໬Ꮫࡀኻࢃࢀ࡚࠾ࡾࠊșѸ࣮ࣚࢻ࣎ࣟࣥ㓟࡜ࡋ࡚ྲྀࡾฟࡍࡇ࡜ࡀ࡛ࡁࢀࡤࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ࡞࡝࡛ᵝࠎ࡟ㄏᑟྍ⬟࡞᭷⏝࡞୰㛫య࡜࡞ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣ࣓ࢱ࣮ࣞࢺ㌿఩࡛฼⏝ࡉࢀࡓ౛ࡢ࡞࠸ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࡟╔┠ࡋࡓ㸦ᅗ 3㸧ࠋࡇࡢ࢔࣮ࢺ㘒యࡣࢩࢡࣟࣉࣟ࣌ࣥࡢ㧗࠸ṍࡳ࡟ࡼࡾ㧗཯ᛂᛶࢆ♧ࡋᐜ᫆࡟࣓ࢱ࣮ࣞࢺ㌿఩ࡀ㐍⾜ࡍࡿ࡜ᮇᚅࡋࡓࠋࡲࡓࠊ⏕ࡌࡿࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟ࡢ⬺㞳ࡣṍࡳ࡟ࡼࡾ୙฼࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡓࡵࠊșѸ࣮ࣚࢻࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟࡜ࡋ࡚ྲྀࡾฟࡍࡇ࡜ࡀ࡛ࡁࡿ࡜⪃࠼ࡽ࠼ࡿࠋࡑࡢㄏᑟ໬࡟ࡼࡾከ⨨᥮ࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟ࢆ⡆౽࠿ࡘ❧య㑅ᢥⓗ࡟ྜᡂྍ⬟࡟࡞ࡿ࡜ィ⏬ࡋࡓࠋᅗ 3㸬ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢṍࡳ㛤ᨺᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒య࡟ࣁࣟࢤࣥ໬๣ࢆస⏝ࡉࡏࡿࡇ࡜࡛ș−ࣁࣟࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟ࡢ❧య≉␗ⓗ࡞ྜᡂࡀྍ⬟࡜⪃࠼ࡽࢀࡿࠋ2ୖཎグᛕ⏕࿨⛉Ꮫ㈈ᅋ◊✲ሗ࿌㞟, 34㸦2020㸧㻌⤖ᯝ࠾ࡼࡧ⪃ᐹ
1㸬 ⎔≧࣍࢘⣲࢔࣮ࢺ㘒యࡢ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩࡟ࡼࡿⅣ⣲⎔㦵᱁ࡢᵓ⠏᪉ἲ㡯࡟♧ࡋࡓ࢝ࢫࢣ࣮ࢻ཯ᛂࢆ᳨ウࡍࡿࡓࡵࠊࡲࡎ⎔≧ࣅࢽࣝ࣎ࣟࣥ㓟ࡢྜᡂࢆヨࡳࡓࠋᙜึࠊȚ఩࡟ࢩ࢔ࣀᇶࢆᣢࡘ࢔ࣜࣝ࢔ࣝࢥ࣮ࣝ࡜ࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࡜ࡢࣜ࢞ࣥࢻ஺᥮㸭㛢⎔࣓ࢱࢭࢩࢫ㹙7㹛࡛ྜᡂ࡛ࡁࡿ࡜ィ⏬ࡋ࡚࠸ࡓࡀ㸦ᅗ 2㸧ࠊ」㞧࡞ΰྜ≀࠾ࡼࡧཎᩱࡀᅇ཰ࡉࢀࡿࡢࡳ࡛࠶ࡗࡓࠋ␗࡞ࡿ⤒㊰ࢆ᳨ウࡋࡓ࡜ࡇࢁࠊపཎᏊ౯ࢳࢱࣥࢆ
⏝࠸ࡿ࢔ࣝ࢟ࣥ࡜࢔ࣝࢹࣄࢻࡢ㑏ඖⓗ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾప཰⋡࡞ࡀࡽ┠ⓗ≀ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ 4a㸧ࠋࡲࡓࠊ ෆᒣࡽࡢ᪉ἲࢆ㹙8㹛ཧ⪃࡜ࡋࠊࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡼࡾࢺࣛࣥࢫࢪ࣎ࣜࣝయࢆⰋዲ࡞཰⋡࡛ྜᡂ࡛ࡁࡓ㸦ᅗ 4b㸧ࠋᅗ 4㸬࢔ࣝࢥ࢟ࢩࢻࡢ㓄఩ࢆ฼⏝ࡍࡿ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࡢヨࡳa㸧 పཎᏊ౯ࢳࢱࣥࢆ⏝࠸ࡿ࢔ࣝࢣࢽࣝ࣎ࣟࣥ㓟ࡢྜᡂࠋb㸧 ࢺࣛࣥࢫࢪ࣎ࣜࣝ໬࡟ࡼࡿ࢔ࣝࢣࢽࣝ࣎ࣟࣥ㓟ࡢྜᡂࠋc㸧 ࢩ࢔ࣀ࢝ࣝࣂࢽ࢜ࣥࡢⓎ⏕࡜ PhSeCl ࢆ⏝࠸ࡿ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࡢヨࡳࠋ஧✀㢮ࡢ⎔≧࣎ࣟࣥ㓟ࡀᚓࡽࢀࡓࡓࡵࠊィ⏬ࡋࡓ࣓ࢱ࣮ࣞࢺ㌿఩ࢆヨࡳࡓ㸦ᅗ 4c㸧ࠋ࣎ࣟࣥ㓟ࢆ⬺Ỉ᮲௳ୗ࢖ࢯ  ࣉࣟࣆ࢚ࣝࢫࢸࣝ࡜ࡋࠊ⁐፹஺᥮ࡢࡢࡕ⢭〇ࡍࡿࡇ࡜࡞ࡃᙉሷᇶࢆస⏝ࡉࡏࡓࠋࢩ࢔ࣀ࢝ࣝࣂࢽ࢜ࣥࡢ⏕ᡂ࡜⎔໬࡛࣎ࣛࢧ࢖ࢡࣝࢆᙧᡂࡋࡓࡢࡕࠊࢭࣞࣥ໬๣㸦PeSeCl㸧ࢆồ㟁Ꮚ๣࡜ࡋ࡚㹙9㹛࣓ࢱ࣮ࣞࢺ㌿఩ࢆᘬࡁ㉳ࡇࡑ࠺࡜ヨࡳࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊཎᩱࡀᅇ཰ࡉࢀࡿࡤ࠿ࡾ࡛࠶ࡾࠊ⌧ᅾࡢ࡜ࡇࢁ┠ⓗࡢ㌿఩ࡀ㐍⾜ࡋࡓࢩࢡࣟ࣌ࣥࢱࣥ⎔ࢆᚓࡿࡇ࡜ࡣ࡛ࡁ࡚࠸࡞࠸ࠋ཯ᛂ᮲௳ࡢ⢭ᰝࢆ⥅⥆୰࡛࠶ࡿࠋࡇࡢࡼ࠺࡟ࠊணᐃࡋࡓ࢔ࣝࢥ࢟ࢩࢻ࡟ࡼࡿไᚚࡀᅔ㞴࡛࠶ࡿࡇ࡜ࡀ ࢃ࠿ࡗࡓࡓࡵࠊࡲࡎࡣࢩࣥࣉࣝ࡞⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࢆ᳨ウࡍࡿࡇ࡜࡜ࡋࡓࠋㄪ〇ࡢᐜ᫆ࡉ࡜ࠊࢥ࣓࣮ࣥ࣍ࢩࣙࣥᅛᐃ࡟ࡼࡿ⎔໬ࡢຠ⋡໬ࢆ⪃࠼ࠊ࣋ࣥࢮࣥ⎔ࢆ᭷ࡍࡿᇶ㉁ࢆࢹࢨ࢖ࣥࡋ   ࣓ࢱ࣮ࣞࢺ㌿఩ࢆヨࡳࡓ㸦ᅗ 5㸧ࠋᇶ㉁࡜࡞ࡿࢩ࢔ࣀ࣓ࢳࣝᇶ࡜ࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆ㐺ษ࡞఩⨨࡟ేࡏᣢࡘ  ໬ྜ≀ࡣ㕥ᮌ̿ᐑᾆ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡗ࡚⡆౽࡟ྜᡂ࡛ࡁࡓࠋNC
C3H7B(pin)i) LHMDS, –78 °Cii) PhSeCl, –78 °C
THF

NOO LiBC3H7SePh

NC

B(pin)
C3H7NCSePh
C3H7SePh

B(pin)

Clca. 30%

byproductᅗ 5㸬PhSeCl ࢆồ㟁Ꮚ๣࡜ࡍࡿ⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ศᏊෆ࡟ࢩ࢔ࣀᇶࢆᣢࡘࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆሷᇶᛶ᮲௳ୗ࡛࣎ࣛࢧ࢖ࢡࣝ࡜ࡋࠊPhSeCl ࡜཯ᛂࡉࡏࡿࡇ࡜࡛⎔⦰ᑠᆺ࣓ࢱ࣮ࣞࢺ㌿఩ࡀ㐍⾜ࡋ࢖ࣥࢲࣥ㦵᱁ࢆᣢࡘ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡀᚓࡽࢀࡓࠋ3ୖཎグᛕ⏕࿨⛉Ꮫ㈈ᅋ◊✲ሗ࿌㞟, 34㸦2020㸧㻌ࡇࢀ࡟ᑐࡋࣜࢳ࣒࢘㸦ࣅࢫࢺ࣓ࣜࢳࣝࢩࣜࣝ㸧࢔࣑ࢻ㸦LHMDS㸧ࢆస⏝ࡉࡏࡿࡇ࡜࡛ࢩ࢔ࣀ࢝ࣝࣂࢽ࢜ࣥࢆⓎ⏕ ࡉࡏࠊ⎔໬࡟ࡼࡾࣅࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࢆㄪ〇ࡋࡓࠋࡇࡢ୰㛫య࡟ࢭࣞࣥ໬๣ࢆస⏝ࡉࡏࡓ࡜ࡇࢁࠊ┠ⓗࡢ⎔⦰ᑠᆺࡢ㌿఩ࡀ㐍⾜ࡋࠊ୕㐃⥆❧య୰ᚰࢆᣢࡘ㧗ᐦᗘ࡟ᐁ⬟ᇶ໬ࡉࢀࡓ࢖ࣥࢲࣥࢆᚓࡿࡇ࡜࡟ᡂຌࡋࡓࠋ1 ࡘࡢ❧య␗ᛶయࡀ୺⏕ᡂ≀࡜ࡋ࡚ᚓࡽࢀ࡚࠾ࡾࠊ㌿఩ࡢ❧య≉␗ᛶࡢࡳ࡞ࡽࡎࠊࢩ࢔ࣀᇶࡢ❧య໬Ꮫࡀồ㟁Ꮚ๣ࡢ཯ᛂ㠃ࢆ ࢥࣥࢺ࣮ࣟࣝࡋ࡚࠸ࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋ⌧ᅾࡢ࡜ࡇࢁࠊࢩ࢔ࣀ࢝ࣝࣂࢽ࢜ࣥࡀࢭࣞࣥ໬๣࡜཯ᛂࡋࡓ๪⏕ᡂ≀ࡢ⏕ᡂࢆᢚ࠼ࡽࢀ࡚࠾ࡽࡎࠊ཯ᛂ᮲௳ࡸᇶ㉁ࡢ⢭ᰝ࡟ࡼࡿ᭱㐺໬ࡀㄢ㢟࡛࠶ࡿࠋ2㸬ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢṍࡳ㛤ᨺᆺ࣓ࢱ࣮ࣞࢺ㌿఩཯ᛂࡢ㛤Ⓨ࣓ࢱ࣮ࣞࢺ㌿఩ࢆ᳨ウࡍࡿࡓࡵࠊࡲࡎࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࡢྜᡂ࠿ࡽ᳨ウࢆ㛤ጞࡋࡓ㸦ᅗ 6㸧ࠋࣅࢽࣝࣈ࣑ࣟࢻ࠿ࡽᐜ᫆࡟ᚓࡽࢀࡿࢺࣜࣈࣟࣔࢩࢡࣟࣉࣟࣃࣥ࡟ᑐࡋࠊࣈࢳࣝࣜࢳ࣒࢘ࢆస⏝ࡉࡏࢩࢡࣟ ࣉࣟ࣌ࢽࣝࣜࢳ࣒࢘ࢆㄪ〇ࡋࡓࠋࡇࡇ࡟࣍࢘㓟࢚ࢫࢸࣝࢆຍ࠼ࡿࡇ࡜࡛ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟ࡢྜᡂࢆヨࡳࡓࡀ⏕ᡂ≀ࡀ୙Ᏻᐃ࡛࠶ࡿࡓࡵ࠿┠ⓗ≀ࢆᚓࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋࡑࡇ࡛ୖグࡢࣜࢳ࢜໬య࡟┤᥋࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆຍ࠼ࡿࡇ࡜࡛ࠋ࢔࣮ࢺ㘒య࡜ࡋࠊࡑࡢࡲࡲồ㟁Ꮚ๣࡜཯ᛂࡉࡏࡿࡇ࡜࡜ࡋࡓࠋࣁࣟࢤࣥ໬๣࡜ࡋ࡚ࣚ࢘⣲ࢆồ㟁Ꮚ๣࡜ࡋ࡚཯ᛂࢆヨࡳࡓࡀࠊ┠ⓗࡢ࣓ࢱ࣮ࣞࢺ㌿఩ࡣ㉳ࡇࡽࡎࠊࣅࢽ࣮ࣝࣚࢪࢻࡢࡳࡀᚓࡽࢀࡓࠋᵝࠎ࡞ࣁࣟࢤࣥ໬๣ࡸ཯ᛂ᮲௳ࢆ᳨ウࡋࡓࡀྠᵝࡢ⤖ᯝ࡟⤊ࢃࡗࡓࠋ୍᪉ࠊồ㟁Ꮚ๣ࢆࢭࣞࣥ໬๣࡬࡜ኚ᭦ࡋࡓ࡜ࡇࢁࠊ┠ⓗࡢ࣓ࢱ࣮ࣞࢺ㌿఩ࡀ㐍⾜ࡋ cisѸșѸࢭࣞࣀࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟ࢆ༢୍ࡢ␗ᛶయ࡜ࡋ࡚Ⰻዲ࡞཰⋡࡛ᚓࡿࡇ࡜࡟ᡂຌࡋࡓࠋᮏ཯ᛂࡣ  ᵝࠎ࡞࣎ࣟࣥ㓟࢚ࢫࢸࣝ࡟㐺⏝ྍ⬟࡛࠶ࡾࠊᵝࠎ࡞࢔࣮ࣜࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡸࠊ࢔ࣝ࢟ࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆ⏝࠸࡚ࡶᑐᛂࡍࡿ㌿఩యࢆ༢୍ࡢ␗ᛶయ࡜ࡋ࡚୚࠼ࡿࠋࡲࡓࠊࢺࣜࣈࣟࣔࢩࢡࣟࣉࣟࣃࣥᇶ㉁࡜ࡋ࡚ࡶᵝࠎ࡞⨨᥮ᇶࢆ⏝࠸ࡿࡇ࡜ࡀ࡛ࡁ࢔ࢲ࣐ࣥࢳࣝᇶࡢࡼ࠺࡞ᔞ㧗࠸⨨᥮ᇶࢆᣢࡗ࡚࠸࡚ࡶၥ㢟࡞ࡃ཯ᛂࡀ㐍⾜ࡋࡓࠋࡲࡓࠊ⦰⎔ᵓ㐀ࢆᣢࡘ  ࡶࡢ࡛ࡣࢩࢡࣟࣉࣟ࣌ࢽࣝᇶࡢ㠃㑅ᢥⓗ࡟཯ᛂࡀ㐍⾜ࡋࠊ୕㐃⥆❧య୰ᚰࢆᣢࡘ࣎ࣟࣥ㓟ㄏᑟయࢆ༢୍ࡢ␗ᛶయ࡜ࡋ࡚୚࠼ࡓࠋ⌧ᅾࠊ⏕ᡂ≀࡛࠶ࡿșѸࢭࣞࣀࢩࢡࣟࣉࣟࣆࣝ࣎ࣟࣥ㓟ࡢㄏᑟ໬ࢆ᳨ウࡋ࡚࠾ࡾࠊィ⟬໬Ꮫࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢ᥈⣴࡜࡜ࡶ࡟ㄽᩥᢞ✏ணᐃ࡛࠶ࡿࠋ
Brn-BuLi(2 eq.)

BrBrLiLiOR
B OR

R B(pin)
MeO

Ph

PhSeCl(pin)B OiPr
M

Br

B(pin)MeOOR
B ORSePhPhPhPh

Ph

CHBr3, NaOH
cat. BnNEt3Cl

II2MeOSePh

Cl66%

Ph௦⾲ⓗ䛺ྜᡂ౛

R= PhCH2CH2–

CF3B(pin)

Ph

Ph

MeO

MeO

OTBS
B(pin)MeO

B(pin)

SePh

74%

R

B(pin)

O

SePh

SePh

71%

R

B(pin)

40%

R

B(pin)

SePh

55%

R

B(pin)
H

SePh

37%

Ad

67%

ᅗ 6㸬ࢩࢡࣟࣉࣟ࣌ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝ࢔࣮ࢺ㘒యࢆ⏝࠸ࡿ࣓ࢱ࣮ࣞࢺ㌿఩ࢺࣜࣈࣟࣔࢩࢡࣟࣉࣟࣃࣥ࠿ࡽⓎ⏕ࡉࡏࡓࢩࢡࣟࣉࣟ࣌ࢽࣝࣜࢳ࣒࢘࡟࣎ࣟࣥ㓟࢚ࢫࢸࣝࢆຍ࠼ࡿࡇ࡜࡛࢔࣮ࢺ㘒యࢆㄪ〇ࡋࠊồ㟁Ꮚ๣࡜ࡋ࡚PhSeClࢆຍ࠼ࡿࡇ࡜࡛❧య≉␗ⓗ࡞࣓ࢱ࣮ࣞࢺ㌿఩ࡀ㐍⾜ࡋࡓࠋ4SePhୖཎグᛕ⏕࿨⛉Ꮫ㈈ᅋ◊✲ሗ࿌㞟, 34㸦2020㸧㻌ㅰ ㎡ᮏ◊✲ࡣᒸᒣ኱Ꮫ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉ᛂ⏝໬Ꮫᑓᨷ⏕≀᭷ᶵ໬Ꮫ◊✲ᐊ࡛⾜ࢃࢀࡓࡶࡢ࡛࠶ࡾࠊ◊✲ࡢ㐙⾜࡟ ࠶ࡓࡾ⤊ጞ࡟Ώࡾ㈗㔜࡞ࡈຓゝ࡜ࡈᣦᑟࢆ㈷ࡾࡲࡋࡓᆏ಴ᙲᩍᤵࠊ᪩ᕝ୍㑻෸ᩍᤵ㸦⌧᪥ᮏ኱Ꮫᩥ⌮Ꮫ㒊ᩍᤵ㸧࡟῝ࡃឤㅰ࠸ࡓࡋࡲࡍࠋᮏ◊✲ᡂᯝࡣᙜ◊✲ᐊᡤᒓࡢᏛ⏕ㅖẶࡢດຊ࡟ࡼࡾᚓࡽࢀࡓࡶࡢ࡛࠶ࡾࠊឤㅰ࠸ࡓࡋࡲࡍࠋᩥ ⊩1㸧 Matteson, DS. Stereodirected Synthesis with Organoboranes. Springer. Berlin. 1995.
2㸧 Namirembe S, Morken JP. Reaction of organoboron compounds enabled by catalyst-promoted metalate shifts.
Chem Soc Rev. 2019 Jul 1;48(13):3464-3474. Epub 2019 May 7. PMID: 31062812 DOI: 10.1039/c9cs00180h.
3㸧 Lovinger JL, Morken JP. Recent Advances in Radical Addition to Alkenylboron Compounds. Eur J Org Chem.
2020 May 3;2020(16):2362-2368. Epub 2019 Nov 21. DOI: 10.1002/ejoc.201901600
4㸧 Davenport R, Silvi M, Noble A, Hosni Z, Fey N, Aggarwal VK. Visible-Light-Driven Strain-Increase RingContraction Allows the Synthesis of Cyclobutyl Boronic Esters. Angew Chem Int Ed Engl. 2020 Apr
16;59(16):6525-6528. Epub 2020 Jan 31. PMID: 31912963 DOI: 10.1002/anie.201915409.
5㸧 Hari DP, Abell JC, Fasano V, Aggarwal VK. Ring-Expansion Induced 1,2-Metalate Rearrangements: Highly
Diastereoselective Synthesis of Cyclobutyl Boronic Esters. J Am Chem Soc. 2020 Mar 25;142(12):5515-5520.
Epub 2020 Mar 12. PMID: 32146807 DOI: 10.1021/jacs.0c00813.
6㸧 Armstrong RJ, Aggarwal VK. 50 Years of Zweifel Olefination: A Transition-Metal-Free Coupling. Synthesis.
2017 Aug 1; 49(15): 3323–3336. Epub 2017 Jul 11. PMCID: PMC6376632 DOI: 10.1055/s-0036-1589046
7㸧 Micalizio GC, Schreiber SL. An alkynylboronic ester annulation: development of synthetic methods forapplication to diversity-oriented organic synthesis. Angew Chem Int Ed Engl. 2002 Sep 2;41(17):3272-6. Epub2002 Aug 30. PMID: 12207413 DOI: 10.1002/1521-3773(20020902)41:17<3272::AID-ANIE3272>3.0.CO;2-C
8㸧 Nagashima Y, Hirano K, Takita R, Uchiyama M. Trans-diborylation of alkynes: pseudo-intramolecular strategy
utilizing a propargylic alcohol unit. J Am Chem Soc. 2014 Jun 18;136(24):8532-5. Epub 2014 Jun 3. PMID:24847909 DOI: 10.1021/ja5036754.
9㸧 Armstrong RJ, Sandford C, García-Ruiz C, Aggarwal VK. Conjunctive functionalization of vinyl boronate
complexes with electrophiles: a diastereoselective three-component coupling. Chem Commun (Camb). 2017
May 2;53(36):4922-4925. Epub 2017 Apr 20. PMID: 28425511 DOI: 10.1039/c7cc01671a.

5