Page 241 - 《精细化工》2023年第4期

す 4 ᱌ 䧌⦉㏏喑ぶ: CuI ϸᄩ Reformatsky ࣺᏁ倅᩵व᜽ ȕ-㓌ധ䚜ㆨࡃव➖ g927g

⩞㶕 4 जⴒ喑ࣺᏁ㐀᳉̻㠜⩟䛈Ⱕѩ喑㠜Ά䚛 Ꮑ [24-25] 喑Ĕa 㣤ᓄࢂ⩢ၽ≨ࡃᒏ᜽̭͗㜗⩞ധ䭡⻨
㟠⣜̷ःАധ⮱⩢䉌ᕔᄦϔ➖ϔ⢴ᰶ䒰᭫㦄⮱ᒞ ၽ͚䬡Ҁ A喑ᣒⱭ͚䬡Ҁ A ౕ CF 3 CO 2 H ҉⩕̸㙞ࣨ
৺喑㟠⣜̷ᰶ॥⩢ၽധఏᬣ喑ϔ➖ϔ⢴䒰ສ喍Ꮌत ⷅ䉌⻨ၽ [16] ϔ⩌̭͗㜗⩞ധ B হ HI喑♣ऻ B 䔈ᩨ
7~12喎ȡ㟠⣜̷ःАധ⮱Ѻ㒛ᄦϔ➖ϔ⢴Όᰶᒞ৺喑 㟠䛈喍ē喎/㟠䚛喍ĕ喎⮱㓝ധⷠϔ⩌ओ̭͗㜗⩞ധ
㟠⣜̷ᄦѺᰶःАധᬣ喑ϔ➖ϔ⢴ᰡສ喍Ꮌत 4Ƞ5Ƞ ͚䬡Ҁ C喑♣ऻౕ䨹҉⩕̸喍䨹᣽ӈࢂ⩢ၽ喎喑͚䬡
8)ȡ㔹㟠⣜̷䗨/䬡ѺᰶःАധᬣ喑ϔ➖ϔ⢴ᰡጛ喍Ꮌ Ҁ C 㣤ᓄ̭͗ࢂ⩢ၽࣾ⩌䔅ࣺ࣌Ꮑ喑⩌᜽䚴⅔䉌⻨
2
त 2Ƞ3Ƞ6)ȡ㔹㟠䚛⮱ R ͧΆധ喑ϔ➖ϔ⢴䒰ጛ喍Ꮌ ၽ D喑ᰭऻౕⅡႅ̸ౕ喑͚䬡Ҁ D 㐀वⅡ͚䉕ၽᓄ
त 18)喑ज㘪᭜Άധ⮱Ѻ䭨䒰๔ᄦࣺᏁ̺ݖȡ⩞λ⏡ ݝᰭ㏵ϔ➖ 1~32ȡCF 3 CO 2 H ⮱ߍڒ㘪ߍ䕌䚴⅔䉌⻨
А㠜Ά䚛⮱⏣㼐ᕔ̺ສ喑ᄩ㜡㟠⣜̷ःАധͧ⏡ᬣ喑 ၽ D 㐀व䉕ၽ⩌᜽ϔ➖ 1~32 䔆̭ₒࣺᏁ [16] ȡ
ϔ➖ϔ⢴䒰ጛ喍Ꮌत 13Ƞ14喎ȡᒀ㟠⣜ͧ㥅⣜Ƞந
ॖ⣜Ƞॎણ⣜ᬣ喑ϔ➖Ό㣤ᓄγ㞜ສ⮱ϔ⢴喍Ꮌत
15~17喎ȡहᵤ喑2-ⷅ-2,2-ι⅌АΆ䚥Ά䚜Ό㘪̻㠜
Ά䚛ࣺᏁ喑́ϔ➖㣤ᓄγх⻭⮱ϔ⢴喍Ꮌत 19喎ȡ
ͧγ侹䃮 CuI ͧϸᄩȠ䨹ㆶͧיࡃݯ⮱יࡃҀ
㈨⮱჋⩕ᕔ喑䔈㵹γٸ㏔㻱὎ࣺᏁȡౕ 1.0612 g
喍10 mmol喎ēaȠ3.2100 g喍15 mmol喎ĔaȠ1.950 g
喍30 mmol喎䨹ㆶȠ3.8020 g喍2 mmol喎CuIȠ148.5 ȝL ఫ 1 ज㘪⮱ࣺᏁᱧ⤳
Fig. 1 Possible reaction mechanism
喍2 mmol喎CF 3 CO 2 HȠ20 mL V(Ά㙵)ńV(ࣨ⻨ၽ
Ⅱ)=1ń1 ⮱⌤व⋟ͧ⏣ݯ⮱᲎У̸ბ⍖ࣺᏁ喑В
92%ϔ⢴㣤ᓄγࡃव➖ 1ȡ 3 㐀䃧
2.3 ࣺᏁᱧ⤳
᱙᪴㔰ᄌγ CuI ϸᄩ喑䨹ㆶיࡃ⮱ 2-ⷅΆ䚥Ά
ͧγ㣤ᓄ䄒יࡃ䓴⼸⮱ᰡ็㏳㞯喑䔈㵹γᄦ⚔
䚜̻̺ह㟠䛈/㟠䚛⮱ Reformatsky ࣺᏁȡ䕇䓴ᄦχ
჋侹喑㐀᳉㻮㶕 5ȡ
䨉⯽⮱よ䔶喑ࣾ⣝䮼Ɑχ䨉⯽͚࢑࣌ၽࡷᒱ෋ߍχ
㶕 5 ᄦ⚔჋侹 䨉⯽⮱יࡃ᩵᳉ᰡສ喑ᒀВ CuI ͧϸᄩᬣ喑ϔ➖ϔ
Table 5 Control experiment
⢴ᰭ倅喠䔈̭ₒᄦ⏣ݯ䔈㵹γよ䔶喑ࣾ⣝ⅡᄦΆ㙵
Ꮌत 䛾ᆋ ⏣ݯ ⌨ߍ➖ ϔ⢴/%
ͧ⏣ݯ⮱㠜⩟䛈喍1.0 mmol喎হ 2-ⷅΆ䚥Ά䚜⮱ࣺ
1 Zn Ά㙵 ᬍ 26 Ꮑ㘪䊤ݝᒵສ⮱Ӱ䔈҉⩕喑́㘪Ხ๔ౝۼᄾࣺᏁᬣ
2 Zn V(Ά㙵)ńV(Ⅱ)=1ń1 ᬍ 48
3 Zn V(Ά㙵)ńV(Ⅱ)=1ń1 CF 3CO 2H 73 䬡喑В 2 mL V(Ά㙵)ńV(Ⅱ)=1ń1 ⮱⌤व⋟ͧ⏣ݯ
4 CuI V(Ά㙵)ńV(Ⅱ)=1ń1 CF 3CO 2H 0 ᬣ喑ϔ➖ϔ⢴ᰭສ喠हᬣࣾ⣝ाࣺᏁҀ㈨͚ߍڒ
5 Zn+CuI V(Ά㙵)ńV(Ⅱ)=1ń1 CF 3CO 2H 94 CF 3 CO 2 H 㘪᭫㦄᣽倅ϔ➖ϔ⢴ȡВ 0.2 mmol CuI ͧ
∕喟ࣺᏁ᲎Уͧ 1.0 mmol ēaȠ1.5 mmol ĔaȠ3.0 mmol Zn ϸᄩȠ3.0 mmol 䨹ㆶͧיࡃݯȠ2 mL V(Ά㙵)ńV(Ⅱ)
ㆶȠ0.2 mmol CuIȠ0.2 mmol CF 3CO 2HȠ2 mL ⏣ݯ喑ბ⍖ࣺᏁȡ =1ń1 ⮱⌤व⋟ͧ⏣ݯ喑ౕ CF 3 CO 2 H ⮱Ӱ䔈̸喑倅

仃ٵ喑ౕ 2 m Ά㙵͚ბ⍖̸喑В䨹ㆶͧיࡃݯ喑 ϔ⢴喍82%~95%喎ౝव᜽γ̭㈨݄ ȕ-㓌ധ䚜 1~32ȡ
⇎ᰶߍڒχ䨉⯽হ CF 3 CO 2 H ᬣ喑ࡃव➖ 1 ग㣤ᓄγ 䄒ࣺᏁ䓫ݝγٸ㏔㻱὎喑ͧ ȕ-㓌ധ䚜⮱ጒ͇ࡃव᜽
26%ϔ⢴喍Ꮌत 1喎ȡ♣ऻ喑ិΆ㙵ᢏ᜽ 2 mL V(Ά ᣽ӈγݺ᱌⮱ᄼ䄂჋侹ᩜᠮȡ
㙵)ńV(Ⅱ)=1ń1 ⮱⌤व⋟喑ϔ➖ϔ⢴᣽倅㜠 48%喑
࣯㔰᪴⡛喟
㶕ᬻⅡ⮱ႅౕᄦϔ➖ϔ⢴ᰶݖ喍Ꮌत 2喎ȡाҀ㈨͚
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ߍڒ CF 3 CO 2 H喑ࣾ⣝ϔ➖ϔ⢴ᰶγ᭫㦄᣽倅喍Ꮌत the ring-closing metathesis for the construction of the solomonamide
3喎ȡ䔈̭ₒⵁ⾣ࣾ⣝喑В 2 mL V(Ά㙵)ńV(Ⅱ)=1ń macrocyclic core: Identification of bioactive precursors[J]. The
Journal of Organic Chemistry, 2018, 83(10): 5365-5383.
1 ͧ⏣ݯȠ䨹ㆶͧיࡃݯȠCF 3 CO 2 H ͧ⌨ߍݯ喑ߍ [2] GOMEZ P A, ROMEA P, URPI F. Stereoselective oxidation of
ڒ CuI 㘪᭫㦄᣽倅ϔ➖ϔ⢴ [24] 喑䓫ݝ 94%喍Ꮌत 5喎ȡ titanium(Ė) enolates with oxygen[J]. Synthesis, 2018, 50(14): 2721-
2726.
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Secondary metabolites isolated from the amazonian endophytic
㐀व̷䔝 CuI ͧϸᄩ喑䨹ㆶיࡃ̺ह㟠䛈喍ē喎 fungus Diaporthe sp. SNB-GSS10[J]. Journal of Natural Products,
/㟠䚛喍ĕ喎̻Ĕ⮱ Reformatsky ࣺᏁ㐀᳉ࣷⰥڠ᪴ 2015, 78(7): 1735-1739.
[4] NAKAMUKAI S, TAKADA K, FURIHATA K, et al. Stellatolide H,
⡛្䖀 [23-25] 喑᣽ܧγ̭͗ज㘪⮱ᱧݣ喑㻮ఫ 1ȡ仃 a cytotoxic peptide lactone from a deep-sea sponge Discodermia
ٵ喑⩞䨹ㆿ᣽ӈࢂ⩢ၽ喍ᝃ䕇䓴䨹䨉⩢֣喎ᑂࣺࣾ sp.[J]. Tetrahedron Lett, 2018, 59(26): 2532-2536.
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