Addition Reaction of Heteroatom Nucleophiles onto Styrene Catalyzed by Ru(II) Complex
Yohei OE*, Tetsuo OHTA*, and Yoshihiko ITO**
(Received May 11, 2009)
Development of a novel Ru(II) complex-catalyzed addition reaction of heteroatom nucleophiles onto styrene was achieved.
Thus, the reaction of N-methyltosylamide with styrene was carried out in the presence of 1 mol% Ru of catalysis generated by mixing [(p-cymene)RuCl2]2, AgOTf and DppBz in CHCl3 at reflux for 18 h to give N-methyl-N-(1-phenylethyl)tosylamide in 83%
yield. NMR experiments, FAB-MS spectrum and X-ray analysis revealed that [(p-cymene)RuOTf(DppBz)]OTf was generated in situ by mixing [(p-cymene)RuCl2]2, AgOTf and 1,2-bis(diphenylphosphino)benzene (DppBz) in refluxed CHCl3. Isolated [(p-cymene)RuOTf(DppBz)]OTf showed good catalytic activity for the addition reaction of N-methyltosylamide, 4-ethylbenzoic acid, and 2-phenylethanol onto styrene in CHCl3 to provide the corresponding addition products in good to excellent yields.
.H\ZRUGV ruthenium catalysis, nucleophilic addition reaction, olefins, atom economy
࣮࣮࢟࣡ࢻ㸸ࣝࢸࢽ࣒࢘ゐ፹㸪ồ᰾ຍᛂ㸪࢜ࣞࣇࣥ㸪ࢺ࣒࢚ࢥࣀ࣑࣮
౯ࡢࣝࢸࢽ࣒࢘㘒యࢆ⏝࠸ࡓ࣊ࢸࣟồ᰾ࡢࢫࢳࣞࣥࡢຍᛂ
Ụὒᖹ࣭ኴ⏣ဴ⏨࣭ఀ⸨ᙪ
ࡣࡌࡵ
ࣝࢥ࣮ࣝ㢮㸪࢚࣮ࢸࣝ㢮㸪࢚ࢫࢸࣝ㢮࠾ࡼࡧ
࣑ࣥ㢮ࡣ㸪᭷ᶵྜᡂᏛୖ㔜せ࡞ྜᡂ୰㛫యࡸ᭱⤊
⏕ᡂ≀ࡋ࡚㸪ᖜᗈ࠸⏝㏵ࢆ᭷ࡍࡿ㔜せ࡞ྜ≀࡛
࠶ࡾ㸪ࡑࢀࡽࢆ⡆౽ࡘຠ⋡ⓗㄪ㐩ࡍࡿᡭἲࡢ㛤
Ⓨࡣ㠀ᖖ㔜せ࡞ㄢ㢟࡛࠶ࡿ㸬ᚑ᮶㸪ࡇࢀࡽࡢྜ
≀ࡣࡋ࡚ồ᰾ⓗ⨨ᛂࡼࡗ࡚ྜᡂࡉࢀ࡚
ࡁࡓࡀ㸪ᑡ࡞ࡃࡶ┠ⓗࡢྜ≀➼ࣔࣝ㔞ࡢᗫᲠ
≀ࡀ⏕ࡋ࡚ࡋࡲ࠺ࡓࡵ㸪ࡑࢀࡽྲྀࡗ࡚᭰ࢃࡿᡭ ἲࡢ㛤Ⓨࡀồࡵࡽࢀࡿ1)㸬࢜ࣞࣇࣥ㢮ࡣ▼Ἔ㈨※
ࡢ➨୍ḟ୰㛫ཎᩱࡋ࡚㇏ᐩᚓࡽࢀ㸪⌧௦࡛ࡶ▼
ἜᏛᕤᴗࡢ୰᰾ࢆᢸ࠺ධᡭᐜ᫆࡞ྜᡂཎᩱࡢ୍
ࡘ࡛࠶ࡿ 2)㸬ࡑࡢࡼ࠺࡞࢜ࣞࣇࣥ㢮ࡽࡢࣝࢥ
࣮ࣝ㢮㸪࢚࣮ࢸࣝ㢮㸪࢚ࢫࢸࣝ㢮࠾ࡼࡧ࣑ࣥ㢮ࡢ
ྜᡂἲࡣ㸪ᙉ㓟ࢆゐ፹ࡍࡿồ᰾ࡢຍᛂࡀ▱
ࡽࢀ࡚࠸ࡿ㸬ࡇࡢᛂ࡛ࡣ㸪ຍ࠸࠺ᛂᙧᘧ
ࡽཎᏊࡢᦆኻࡀ࡞ࡃࢺ࣒࢚ࢥࣀ࣑࣮ඃࢀ࡚࠾
ࡾ⨨ᛂẚ࡚⎔ቃ㐺ᛂࡋࡓࡶࡢゝ࠼ࡿ㸬 ࡋࡋ࡞ࡀࡽ㸪ゐ፹㔞࠸࠼ࡶᙉ㓟ࢆ⏝࠸ࡿࡓࡵ㸪 ᕤᴗࡍࡿࡣ⎔ቃࡸタഛࡢ㈇Ⲵࡀၥ㢟࡛࠶ࡿ㸬
୍᪉㸪㑄⛣㔠ᒓ㘒యࢆ⏝࠸ࡓᆒ୍⣔ゐ፹ᛂࡣ㸪 ࡈࡃᑡ㔞ࡢ㘒యゐ፹ࢆ⏝࠸㸪୰ᛶࡢ᮲௳ୗ࠾࠸࡚
* Department of Biomedical Information, Faculty of Life and Medical Sciences, Doshisha University, Kyoto Yohei OE; Telephone: +81-774-65-6505, FAX: +81-774-65-6505, E-mail: [email protected] Tetsuo OHTA; Telephone: +81-774-65-6548, FAX: +81-774-65-6789, E-mail: [email protected]
** Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University
ከᵝ࡞ᛂࢆไᚚ࡛ࡁࡿ࠸ࡗࡓⅬ࡛㸪⌧ᅾ᭱ࡶά
Ⓨ◊✲ࡉࢀ࡚࠸ࡿศ㔝ࡢ୍ࡘ࡛࠶ࡿ㸬㑄⛣㔠ᒓ㘒 యࢆ⏝࠸ࡓ࣊ࢸࣟồ᰾࢜ࣞࣇࣥࡢᛂࡋ
࡚Wackerᛂࡀᣲࡆࡽࢀࡿࡀ㸪EỈ⣲⬺㞳ࢆ㉳ࡇ
ࡍࡇࡽ༢⣧࡞ຍ⏕ᡂ≀ࡣᚓࡽࢀ࡞࠸3)㸬ࢆ
㏉ࡏࡤ㸪EỈ⣲⬺㞳ࢆไᚚࡍࡿࡇࡀ࡛ࡁࢀࡤ㸪✜
ࡸ࡞᮲௳࡛ࡢ༢⣧࡞ຍᛂࢆ㐩ᡂ࡛ࡁࡿ㸬ࡑࡢ
ࡼ࠺࡞ほⅬࡽ㸪ᙜ◊✲ᐊ࡛ࡣ㑄⛣㔠ᒓࡢゐ፹స⏝
ࢆ⏝ࡋ㸪࡞࠾ࡘEỈ⣲⬺㞳ࢆไᚚࡍࡿࡇࡼ
ࡗ࡚㸪࢜ࣞࣇࣥࡢ࣊ࢸࣟồ᰾ࡢ༢⣧࡞ຍ
ᛂ㛵ࡍࡿ◊✲ࢆ⥅⥆ࡋ࡚⾜ࡗ࡚ࡁࡓ㸬ࡑࡢ⤖ᯝ㸪 ศᏊෆᛂ࡛ࡣ୕౯ࡢࣝࢸࢽ࣒࢘ 4a-b)㸪౯ࡢ㖡࠾
ࡼࡧ୍౯ࡢ㖟㘒య 5) ࡀ┠ⓗࡍࡿ࢜ࣞࣇࣥࡢ ồ᰾ࡢຍᛂࢆゐ፹ࡍࡿࡇࢆぢฟࡋࡓ㸬≉㸪
ࣝࢸࢽ࣒࢘ゐ፹ࡣࡇࡢᛂᙧᘧ࠾࠸࡚၏୍ᩧ
ᛂࢆᐇ⌧ࡋࡓඃࢀࡓゐ፹⣔࡛࠶ࡿ4b) (Scheme 1)㸬
Scheme 1. Asymmetric Intramolecular Cyclization.
ࡲࡓ㸪ศᏊ㛫ᛂ࡛ࡣ୕౯ࡢࣝࢸࢽ࣒࢘ゐ፹ࡀ࢝
ࣝ࣎ࣥ㓟㢮㸪ࣝࢥ࣮ࣝ㢮࠾ࡼࡧࢫ࣑ࣝ࣍ࣥࢻ㢮 ࡢ࢜ࣞࣇࣥࡢຍᛂࢆゐ፹ࡍࡿࡇࢆぢฟ ࡋ࡚࠸ࡿ6a-b) (Scheme 2)㸬
Scheme 2. Ru(III)-Catalyzed Intermolecular Additions.
ࡋࡋ࡞ࡀࡽ㸪ศᏊ㛫ᛂ࠾ࡅࡿ࢜ࣞࣇࣥࡢ ᇶ㉁㐺⏝⠊ᅖࡣ⊃ࡃ㸪ᇶ㉁୍⯡ᛶᐩࢇࡔゐ፹⣔ࡢ 㛤Ⓨࡀ⌧Ⅼ࠾࠸࡚ࡁ࡞ㄢ㢟࡛࠶ࡿ㸬ゐ፹άᛶ ࡢྥୖࢆᅗࡿࡣ㸪⣔୰࡛ࡢࡼ࠺࡞ゐ፹άᛶ✀ࡀ ᙧᡂࡉࢀ࡚࠸ࡿࢆ▱ࡿࡇࡀ᭱ࡶ㏆㐨࡞ࡿࡀ㸪
୕౯ࡢࣝࢸࢽ࣒࢘㘒యࡣᖖ☢ᛶ࠾ࡼࡧᏳᐃࡉ
ࡽ㸪ࡑࢀࡽࢆྠᐃࡍࡿࡇࡣ㠀ᖖᅔ㞴ࢆᴟࡵࡓ㸬
ᅇᡃࠎࡣ㸪ẚ㍑ⓗྲྀᢅ࠸᫆ࡃ㸪NMR ࡛ࡢほ
ࡶᐜ᫆࡞౯ࡢࣝࢸࢽ࣒࢘ゐ፹⣔ࡢ㛤Ⓨᡂຌࡋ㸪
⣔୰࡛Ⓨ⏕ࡋ࡚࠸ࡿゐ፹άᛶ✀㛵ࡍࡿ㔜せ࡞▱
ぢࡀᚓࡽࢀࡓࡢ࡛௨ୗሗ࿌ࡍࡿ㸬
ヨ⸆࠾ࡼࡧᐇ㦂᪉ἲ ヨ⸆
ᇶ㉁ࡢࢫࢳࣞࣥ㸪N࣓ࢳࣝࢺࢩ࣑ࣝࢻ㸪p࢚ࢳ
ࣝᏳᜥ㤶㓟㸪ࣇ࢙ࢽ࢚ࣝࢱࣀ࣮ࣝ㸪㓄Ꮚࡢࢺࣜ
ࣇ࢙ࢽ ࣝ࣍ࢫࣇ ࣥ㸪Dppm, Dppe, Dppp, Dppb,
DppBz 7)㸪࠾ࡼࡧࢺࣝࣇ࣓ࣝ࢜ࣟࢱࣥࢫࣝ࣍ࣥ㓟㖟
(AgOTf)ࡣᕷ㈍ရࢆ⢭〇ࡍࡿࡇ࡞ࡃࡑࡢࡲࡲ⏝
ࡋࡓ㸬ࢸࢺࣛࢡࣟࣟࣅࢫpࢩ࣓ࣥࢪࣝࢸࢽ࣒࢘㘒 య[(p-cymene)RuCl2]2ࡣ㸪ᩥ⊩グ㍕ࡢ᪉ἲࢆᨵⰋࡋ ࡓ᪉ἲ࡛ㄪ〇ࡋࡓ8)㸬ࢡ࣒ࣟࣟ࣍ࣝ㸪ሷ࣓ࢳࣞࣥ㸪
࠾ࡼࡧ㔜ࢡ࣒ࣟࣟ࣍ࣝ㸪࣊࢟ࢧࣥࡣỈ⣲࢝ࣝࢩ࢘
࣒࡚⬺Ỉᚋ㸪ࣝࢦࣥẼὶୗ࡚ᖖᅽ␃ࡋࡓࡶ
ࡢࢆ⏝ࡋࡓ㸬ࢪ࢚ࢳ࢚࣮ࣝࢸࣝࡣࢼࢺ࣒ࣜ࢘࣋
ࣥࢰࣇ࢙ࣀ࡛ࣥ⬺Ỉᚋ㸪ࣝࢦࣥẼὶୗ࠾࠸࡚ᖖ ᅽ␃ࡋࡓࡶࡢࢆ⏝ࡋࡓ㸬
ᵓ㐀ゎᯒ
NMR ࢫ࣌ࢡࢺࣝࡣ㸪VarianVNMR300 Mercury plus (300 MHz for 1H, 282 MHz for 19F, 125 MHz for
31P) ࢆ⏝࠸࡚ ᐃࡋࡓ㸬FAB-MS ࢫ࣌ࢡࢺࣝࡣ㸪 JEOL Mstation JMS-700ࢆ⏝࠸࡚ ᐃࡋࡓ 㸬
ᐇ㦂᪉ἲ
^SF\PHQH5X&O'SS%]`&O ࡢㄪ〇
ࣇ࣮࣒ࣞࢻࣛᚋ㸪ࣝࢦࣥࢆሸࡋࡓ୕ཱྀᛂ ᐜჾ㸪[(p-cymene)RuCl2]2 (0.0621 g, 0,1 mmol)㸪 DppBz (0.1116 g, 0.25 mmol)㸪CH2Cl2 (10 mL)ࢆຍ࠼㸪 ຍ⇕㑏ὶୗ㸪4.5 㛫ᛂࡉࡏࡓ㸬ᛂ⤊ᚋ㸪⁐
፹ࢆ࠾ࡼࡑ2.5 mL⛬ᗘ࡞ࡿࡲ࡛ῶᅽ␃ཤࡋ㸪3 mL ࡢࢪ࢚ࢳ࢚࣮ࣝࢸࣝࢆຍ࠼࡚ 30 ศ㛫ᨩᢾࡋࡓ㸬ᨩ ᢾ⤊ᚋ㸪⏕ᡂࡋࡓⷧ㯤Ⰽࡢಶయࢆℐྲྀࡋ㸪ṧ´ࢆ
ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ (35 mL)࡛Ὑίࡋ㸪┿✵ୗ࡛
⇱ࡍࡿࡇࡼࡗ࡚㸪┠ⓗࡍࡿ㘒యࡀᚓࡽࢀࡓ㸬 ᚓࡽࢀࡓ㘒యࡣ≉⢭〇ࡍࡿࡇ࡞ࡃ㸪ࡑࡢࡲࡲḟ ࡢᛂ⏝ࡋࡓ㸬
[(p-cymene)RuCl(DppBz)]Cl㸸Light Yellow Solid
1H NMR (300 MHz, CDCl3) G (ppm) = 0.82 (6H, d, J = 6.9 Hz, (CH3)2CH), 1.86 (3H, s, CH3), 2.46 (1H, septet, J
= 6.9 Hz, (CH3)2CH), 6.04 (2H, d, J = 9.6 Hz, ArH of p-cymene), 6.29 (2H, d, J = 9.0 Hz, ArH of p-cymene), 7.03-7.10 (4H, m, ArH), 7.29-7.89 (16H, m, ArH).
31P NMR (125 MHz, CDCl3) G (ppm) = 66.0.
FAB-MS (m/z) 717 [MCl]+.
>SF\PHQH5X27I'SS%]@27I
ࣇ࣮࣒ࣞࢻࣛᚋ㸪ࣝࢦࣥࢆሸࡋࡓ୕ཱྀᛂ ᐜჾ㸪2.3.1࡛ᚓࡽࢀࡓ[(p-cymene)RuCl(DppBz)]Cl㸪 AgOTf (0.1380 g, 0.5 mmol)㸪CHCl3 (15 mL)ࢆຍ࠼㸪 ຍ⇕㑏ὶୗ㸪4.5 㛫ᛂࡉࡏࡓ㸬ᛂ⤊ᚋ㸪
ࣝࢦࣥୗ࡛ࢭࣛࢺࣃࢵࢻࢆ㏻ࡌ࡚ AgClℐูࡋ㸪 ℐᾮࢆ࠾ࡼࡑ0.3 mL⛬ᗘ࡞ࡿࡲ࡛ῶᅽ␃ཤࡋࡓࠋ 5 mLࡢࢪ࢚ࢳ࢚࣮ࣝࢸࣝࢆຍ࠼㸪ᐊ ࡛30ศ㛫ᨩ ᢾࡋࡓᚋ㸪⏕ᡂࡋࡓᶳⰍࡢಶయࢆℐྲྀࡋ㸪ࢪ࢚ࢳࣝ
࢚࣮ࢸࣝ (310 mL)࡛Ὑίࡋࡓ㸬᭱ᚋ㸪┿✵ୗ࡛
⇱ࡍࡿࡇࡼࡗ࡚㸪┠ⓗࡍࡿ㘒యࡀᚓࡽࢀࡓ㸬 X⥺⤖ᬗᵓ㐀ゎᯒ⏝ࡢ༢⤖ᬗࡣ㸪ࢡ࣒ࣟࣟ࣍ࣝ
࣊࢟ࢧࣥࡽᚓࡓ㸬
[(p-cymene)RuOTf(DppBz)]OTf㸸Orange Solid
1H NMR (300 MHz, CDCl3) G (ppm) = 0.78 (6H, d, J = 6.9 Hz, (CH3)2CH), 2.03 (3H, s, CH3), 2.16 (1H, septet, J
= 6.9 Hz, (CH3)2CH), 6.08 (4H, s, ArH of p-cymene), 6.75-6.77 (4H, m, ArH), 7.11-7.69 (16H, m, ArH).
31P NMR (125 MHz, CDCl3) G (ppm) = 61.6.
19F NMR (282 MHz, CDCl3) G (ppm) = -78.4, -78.5.
FAB-MS (m/z) 831 [MOTf]+.
>SF\PHQH5X27I'SS%]@27I ࢆ⏝࠸ࡓࢫࢳ
ࣞࣥࡢ࣊ࢸࣟồ᰾ࡢຍᛂ
ᆺࡋ࡚㸪N-࣓ࢳࣝࢺࢩ࣑ࣝࢻࢫࢳࣞࣥࡢ
ᛂࢆ♧ࡍ㸹80 mLࡢࢩࣗࣞࣥࢡࢳ࣮ࣗࣈࢆࣇ࣮ࣞ
࣒ ࢻ ࣛ ࡋ 㸪 ࣝ ࢦ ࣥ ࢆ ሸ ࡋ ࡓ ᚋ 㸪 [(p-cymene)RuOTf(DppBz)]OTf (19 mg, 0.02 mmol)㸪 N-࣓ࢳࣝࢺࢩ࣑ࣝࢻ (0.1852 g, 1 mmol)㸪ࢫࢳࣞࣥ
(0.27 mL, 2.5 mmol)㸪ࢡ࣒ࣟࣟ࣍ࣝ (2 mL)ࢆຍ࠼ࡓ㸬
ᛂΰྜ≀ࢆຍ⇕㑏ὶୗ㸪48㛫ᛂࡉࡏࡓᚋ㸪⁐
፹ࢆῶᅽ␃ཤࡋ㸪ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ
࣮ (ᒎ㛤⁐፹㸹࣊࢟ࢧࣥ㸸㓑㓟࢚ࢳࣝ = 4 : 1)
࡚┠ⓗ≀ࢆ༢㞳ࡋࡓ㸬
N-methyl-N-(1-phenylethyl)tosylamide㸸White Solid
1H NMR (300 MHz, CDCl3) G (ppm) = 1.28 (3H, d, J = 6.9 Hz, CH3), 2.43 (3H, s, ArCH3), 2.56 (3H, s, N-CH3), 5.28 (1H, q, J = 6.9 Hz, CH), 7.19-7.35 (7H, m, ArH), 7.73 (2H, d, J =8.1 Hz, ArH).
13C NMR (75 MHz, CDCl3) : G (ppm) 142.9, 139.7, 137.0, 129.6, 128.3, 127.4, 127.1, 126.9, 54.7, 28.4, 21.6, 15.2.
FAB-MS (m/z) 289 [M]+.
⤖ᯝ࠾ࡼࡧ⪃ᐹ
௨๓ࡼࡾ౯ࡢࣝࢸࢽ࣒࢘ゐ፹ࢆ⏝࠸ࡓ᳨ウࢆ
⾜ࡗ࡚ࡁࡓࡀ㸪࠸࡞ࡿሙྜ࠾࠸࡚ࡶ౯ࡢࣝࢸ ࢽ࣒࢘㘒యࡶゐ፹๓㥑యࡋ࡚᭷ຠࡣാ࡞
ࡗࡓ㸬ᡃࠎࡣ㸪ࡇࡢせᅉࢆ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒 యࡋࡓ㝿ࡢⰾ㤶᪘⁐፹ࡼࡿ⁐፹ࡀάᛶ
ᘬࡁ㉳ࡇࡋ࡚࠸ࡿ⪃࠼ࡓ㸬ࡍ࡞ࢃࡕ㸪ⰾ㤶᪘ᛶ⁐
፹ࢆ⏝࠸ࡿ㸪AgOTfࡢࢽ࢜ࣥࡼࡾⓎ⏕
ࡋࡓ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒యࡀⰾ㤶᪘⣔⁐፹
ࡼࡗ࡚ࢧࣥࢻࢵࢳᆺࡢࣝࢸࣀࢭࣥ㘒యኚ
ࡋ㸪ゐ፹ࡋ࡚ࡢᶵ⬟ࢆᯝࡓࡉ࡞ࡃ࡞ࡿࡓࡵ࡛࠶ࡿ
ண ࡋࡓ (Scheme 3)㸬
Scheme 3. Predicted Deactivation of Ru Catalysis by Aromatic Solvents.
ࡑࡇ࡛㸪N㸫࣓ࢳࣝࢺࢩ࣑ࣝࢻࢫࢳࣞࣥࡢ
ᛂࢆࣔࢹࣝᛂࡋ㸪ୖグࡢࡼ࠺࡞㈇ࡢຠᯝࡀ࡞
࠸ண ࡉࢀࡿࢡ࣒ࣟࣟ࣍ࣝࢆ⁐፹ࡋ࡚㸪㘒యࡢ
⁐ゎᗘ࠾ࡼࡧᏳᐃᛶࢆᮇᚅࡋ࡚ࢸࢺࣛࢡࣟࣟࣅࢫ(p 㸫ࢩ࣓ࣥ)ࢪࣝࢸࢽ࣒࢘㘒య [(p-cymene)RuCl2]2 ࢆ ゐ፹๓㥑యࡋ࡚㑅ᐃࡋ㸪ᛂ᮲௳ࡢ᳨ウࢆ⾜ࡗࡓ㸬 ࡑࡢ⤖ᯝࢆ㸪Table 1♧ࡍ㸬
Table 1. Optimization of Reaction Conditionsa
Entry Ligand Yield (%)b
1 PPh3 32
2 Dppm 46 3 Dppe 84 4 Dppp 85 5 Dppb 83 6 DppBz 83
a) Reaction conditions: N-methyltosylamide (1mmol), styrene (2.5 mmol), catalyst (0.02 mmol Ru), CHCl3 (2 mL), at reflux, for 18 h. b) Isolated yield.
Table 1ࡽ᫂ࡽ࡞ࡼ࠺㸪ணࡋࡓ㏻ࡾ౯
ࡢࣝࢸࢽ࣒࢘㘒య࡛ࡶ⁐፹ࡼࡗ࡚ゐ፹ࡀኻάࡉ
ࢀ࡞ࡅࢀࡤ㸪ప⋡࡞ࡀࡽࡶᛂࡣ᭷ព㐍⾜ࡍࡿ
(Entry 1)㸬ࡉࡽ㸪㓄Ꮚࢆᗙࡢ࣍ࢫࣇࣥ㓄
Ꮚࡍࡿࡇ࡛㸪80%௨ୖࡢ㧗⋡࡛┠ⓗ≀ࡀᚓࡽ
ࢀࡓ (Entries 2-6)㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪༢ᗙ㓄Ꮚࡢ ࢺࣜࣇ࢙ࢽࣝ࣍ࢫࣇࣥ (PPh3) ࢆ⏝࠸ࡓሙྜ, ᛂ୰ࣝࢸࢽ࣒࢘ࡽࡢ㓄Ꮚࡢゎ㞳ࡀ㉳ࡇࡾ㸪ᇶ
㉁࡛࠶ࡿࢫࢳࣞࣥࡢⰾ㤶⎔ࡀ㸪ⰾ㤶᪘⣔ࡢ⁐፹ྠ
ᵝࡢゐ፹ኻάຠᯝࢆࡶࡓࡽࡋࡓࡓࡵ࡛࠶ࡿ⪃࠼
ࡽࢀࡿ㸬Table 1ࡢ⤖ᯝࡼࡾ㸪౯ࡢࣝࢸࢽ࣒࢘ゐ፹
⣔ࡶ୕౯ࡢࣝࢸࢽ࣒࢘ゐ፹⣔ྠ➼㸪࠶ࡿ࠸ࡣࡑࢀ
௨ୖࡢゐ፹άᛶࢆ᭷ࡍࡿࡇࡀ♧၀ࡉࢀࡓ㸬 ḟ㸪ᡃࠎࡣ⣔୰Ⓨ⏕ࡋ࡚࠸ࡿゐ፹άᛶ✀ࡢゎ
᫂ྲྀࡾ⤌ࢇࡔ㸬ᅇࡢゐ፹ᛂ࡛ࡣ㸪ᛂࡢ๓ẁ 㝵ࡋ࡚[(p-cymene)RuCl2]2AgOTf ࢆస⏝ࡉࡏࡓ
ᚋ㸪DppBzࢆຍ࠼ࡿ࠸࠺ゐ፹ㄪ〇㐣⛬ࡀ࠶ࡿ㸬ࡑ
ࡇ࡛㸪ࡑࡢྛẁ㝵ࢆ1H, 19F࠾ࡼࡧ31P NMRࢆ⏝࠸
࡚㸪⣔୰࡛Ⓨ⏕ࡋ࡚࠸ࡿࣝࢸࢽ࣒࢘㘒యࡢゎ᫂ࢆ࠾
ࡇ࡞ࡗࡓ (Table 2)㸬[(p-cymene)RuCl2]2ࢺࣜࣇࣝ࢜
࣓ࣟࢱࣥࢫࣝ࣍ࣥ㓟㖟 (AgOTf) ࢆ㔜ࢡ࣒ࣟࣟ࣍ࣝ
୰࡚ 3 㛫ᛂࡉࡏࡓᚋ㸪DppBz ࢆస⏝ࡉࡏ㸪 NMRゎᯒࢆ⾜ࡗࡓ㸬Table 2ࡽ᫂ࡽ࡞ࡼ࠺㸪
AgOTf ࡼࡗ࡚ฎ⌮ࡍࡿࡇࡼࡾ㸪 p-ࢩ࣓ࣥ⎔
ୖࡢࣉࣟࢺࣥࡀ᫂ࡽప☢ሙࢩࣇࢺࡋ࡚࠸ࡿࡇ
㸪[(p-cymene)RuCl2]2 ⏤᮶ࡢࢩࢢࢼࣝࡀほ ࡉࢀ
࡞ ࠸ ࡇ ࡀ 1H NMR ࡽ ☜ ㄆ ࡉ ࢀ 㸪 [(p-cymene)RuCl2]2ࡣูࡢ㘒యኚࡋ࡚࠸ࡿࡇ
ࡀ♧၀ࡉࢀࡓ㸬ࡲࡓ㸪ࡑࡢᚋࡢDppBzࢆ⏝࠸ࡓฎ
⌮࠾࠸࡚㸪31P NMR࡛ࡣ㸪ࣝࢸࢽ࣒࢘㓄ࡋ࡚
࠸ࡿ⪃࠼ࡽࢀࡿ DppBz⏤᮶ࡢࣆ࣮ࢡࡀ61.6 ppm
☜ㄆࡉࢀࡓ㸬 ༢ᗙࡢPPh3ࢆ⏝࠸ࡓ㝿ࡢᏛࢩࣇ
ࢺ್ (26 ppm) ẚ࡚ࡁࡃప☢ሙࢩࣇࢺࡋ࡚࠸
ࡿࡓࡵ㸪DppBzࢆ⏝࠸ࡓ㘒యࡣࡘࡢࣜࣥཎᏊࣝ
ࢸࢽ࣒࢘ࢆྵࡴဨ⎔ᵓ㐀ࢆྲྀࡗ࡚࠸ࡿࡇࡀ♧
၀ࡉࢀࡿ9)㸬ࡉࡽ㸪19F NMR࠾࠸࡚㸪-78.4 ppm, -78.5 ppmࡰ1 : 1ࡢ✚ศẚ࡛ᮏࡢࢩࣥࢢࣞࢵ
ࢺࡀ☜ㄆ࡛ࡁࡓ㸬ࡇࡢࡇࡽ㸪୍ࡘࡢOTfࡣࣝࢸ ࢽ࣒࢘㓄ࡋ࡚࠾ࡾ㸪ࡶ࠺୍᪉ࡢOTfࡣ࢝࢘ࣥࢱ
࣮ࢽ࢜ࣥࡋ࡚Ꮡᅾࡋ࡚࠸ࡿࡇࡀ♧၀ࡉࢀࡓ㸬 ௨ୖࡢ⤖ᯝࡼࡾ㸪ୖ㏙ࡢゐ፹ㄪ〇ẁ㝵ࢆ⤒ࡿࡇ
ࡼࡗ࡚㸪 [(p-cymene)Ru(OTf)(DppBz)]OTf ࡞ࡿ㘒య ࡀᙧᡂࡉࢀ࡚࠸ࡿࡇࡀணࡉࢀࡿ㸬
Table 2. Chemical Shifts of Catalyst Generated in situ.
Conditions Chemical Shifts (ppm)
1H NMR 19F NMR 31P NMR Material 5.33, 5.46
After Step 1 5.76, 5.90 -77.5 (br)
After Step 2 6.08 -78.4, -78.5 61.6
FAB-MSࢫ࣌ࢡࢺ࡛ࣝࡢゎᯒࡣࡑࡢணࢆࡅ
ࡿࡶࡢ࡞ࡾ㸪[(p-cymene)Ru(OTf)(DppBz)]+ࡢࣇࣛ
ࢢ࣓ࣥࢺ࢜ࣥࣆ࣮ࢡࡢ831 m/z ࡀ☜ㄆࡉࢀࡓ㸬୍
᪉㸪⣧≀ࡋ࡚AgX (X = OTf or Cl) DppBzࡢ 1 : 2㘒య⪃࠼ࡽࢀࡿ Ag(DppBz)+ࡢศᏊ࢜ࣥࣆ
࣮ࢡ (1001 m/z)ࡶ☜ㄆࡉࢀࡓ㸬
௨ୖ, NMR࠾ࡼࡧMSࢫ࣌ࢡࢺࣝࡼࡿゎᯒࡽ
⪃ ࠼ ࡽ ࢀ ࡿ ᪂ つ ࡢ ࢝ ࢳ ࢜ ࣥ ᛶ ࣝ ࢸ ࢽ ࢘ ࣒ 㘒 య [(p-cymene)Ru(OTf)(DppBz)]OTf ࡢྜᡂ࣭༢㞳ࢆヨ
ࡳࡓ㸬
Scheme 4. Two Step Preparation of
[(p-cymene)Ru(OTf)(DppBz)]OTf.
Scheme 4♧ࡋࡓᵝ㸪㖟㘒య [Ag(DppBz)2]Xࡢ
⏕ ᡂ ࢆ 㑊 ࡅ ࡿ ࡓ ࡵ 㸪 ࡲ ࡎ[(p-cymene)RuCl2]2 DppBzࢆᛂࡉࡏ㸪[(p-cymene)RuCl(DppBz)]Clࢆㄪ
〇ࡋࡓ㸬ḟ࠸࡛㸪ᚓࡽࢀࡓ㘒యࢆᑠ㐣ࡢ AgOTf
࡛ฎ⌮ࡋࡓᚋ㸪ࢪ࢚ࢳ࢚࣮ࣝࢸ࡛ࣝࡼࡃὙίࡍࡿࡇ
࡛㸪┠ⓗࡢ㘒య [(p-cymene)Ru(OTf)(DppBz)]OTf ࡀᚓࡽࢀࡓ㸬ᚓࡽࢀࡓ㘒యࡢNMR࠾ࡼࡧMSࢫ࣌
ࢡࢺࣝࡣୖ㏙ࡢ⣔୰Ⓨ⏕ᐇ㦂࡛ᚓࡽࢀࡓ್ࡼࡃ
୍⮴ࡋࡓ㸬ࡲࡓ㸪ᖾ࠸ࡶᚓࡽࢀࡓ㘒యࡢ༢⤖ᬗࢆ
ࢡ࣒ࣟࣟ࣍ࣝ/࣊࢟ࢧࣥࡽࡢ⤖ᬗࡼࡗ࡚ㄪ〇 ࡍࡿࡇࡀ࡛ࡁ㸪X⥺⤖ᬗᵓ㐀ゎᯒࡼࡗ࡚ࣝࢸࢽ
࣒࢘ࡢྛ㓄Ꮚࡢ㓄ᙧᘧࡣࢫ࣌ࢡࢺࣝゎᯒ
ࡽணࡋࡓࡶࡢ୍⮴ࡋࡓ (Fig 1)㸬
༢㞳ࡋࡓ㘒య[(p-cymene)Ru(OTf)(DppBz)]OTf ࢆ
⏝࠸࡚㸪ࢡ࣒ࣟࣟ࣍ࣝ୰㸪ຍ⇕㑏ὶୗ㸪 p-࢚ࢳࣝᏳ ᜥ㤶㓟㸪2-ࣇ࢙ࢽ࢚ࣝࢱࣀ࣮ࣝ㸪N-࣓ࢳࣝࢺࢩࣝ
Fig 1. ORTEP Structure of
[(p-cymene)Ru(OTf)(DppBz)]OTf.
Scheme 5. Addtion of Heteroatom Nucleophiles onto Styrene Using [(p-cymene)Ru(OTf)(DppBz)]OTf.
࣑ࢻࢫࢳࣞࣥࡢᛂࢆ⾜ࡗࡓ (Scheme 5)㸬ࡑࡢ⤖
ᯝ㸪࠸ࡎࢀࡢሙྜࡶ┠ⓗ⏕ᡂ≀ࡀⰋዲ࡞⋡࡛ᚓࡽ
ࢀࡓ㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪⣔୰࡛ࡣ࢝ࢳ࢜ࣥᛶࣝࢸࢽ
࣒࢘㘒య [(p-cymene)Ru(OTf)(DppBz)]OTf ࡀⓎ⏕
ࡋ㸪ࡑࡢࡀ࢜ࣞࣇࣥࡢ࣊ࢸࣟồ᰾ࡢ࢜ࣞࣇ
ࣥࡢຍᛂࢆ㐍⾜ࡉࡏ࡚࠸ࡿࡇࢆ♧၀ࡍࡿ
ࡶࡢ࡛࠶ࡿ㸬
㸲㸬⤖ㄽ
ᡃࠎࡣ㸪౯ࡢ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒యࡀ࣊ࢸ
ࣟồ᰾ࡢ࢜ࣞࣇࣥࡢຍᛂᑐࡍࡿゐ፹ άᛶࢆ᭷ࡍࡿࡇࢆぢฟࡋࡓ㸬ࡑࡢ୰࡛㸪වࡡ࡚
ࡽࡢᠱ࡛࠶ࡗࡓ⣔୰࡛Ⓨ⏕ࡋ࡚࠸ࡿゐ፹άᛶࢆ
᭷ࡍࡿࣝࢸࢽ࣒࢘✀ࡢᵓ㐀Ỵᐃ࠾ࡼࡧࡑࡢ༢㞳
ࡶᡂຌࡋࡓ㸬
ᮏ◊✲ࢆ㐙⾜ࡍࡿ࠶ࡓࡾ㸪῝࠸⇕ࢆࡶࡗ࡚ᚚ ᣦᑟ࣭ᚚ㠴᧡ࢆୗࡉࡗࡓఀ⸨ᙪᩍᤵࡣ㸪2006 ᖺ 12᭶23᪥㏽ཤࡉࢀࡓ㸬ࡇࡢሙࢆࡾ࡚㸪῝ࡃឤ ㅰࡢពࢆ⾲ࡋ㸪ᚚෞ⚟ࢆ࠾♳ࡾࡍࡿࡶ㸪ྠᩍ
ᤵᮏㄽᩥࢆᤝࡆࡿ㸬
ᮏ◊✲ࡢ୍㒊ࡣ㸪ࠕ⌮ᕤᏛ◊✲ᡤ 2008 ᖺᗘྠᚿ
♫Ꮫ⌮ᕤᏛ◊✲ᡤ◊✲ຓᡂ㔠 (ಶே)ࠖࡢᨭࢆཷ
ࡅࡓ㸬ࡇࡇグࡋ࡚㸪ㅰពࢆ⾲ࡍࡿ㸬
㸳㸬ཧ⪃ᩥ⊩
1) a) B. M. Trost, “The Atom Economy--A Search for Synthetic Efficiency,” Science, 254, 1471 (1991).
b) B. M. Trost, “Atom Economy - A Challenge for Organic Synthesis: Homogeneous Catalysis Leads the Way,” Angew. Chem. Int. Ed. Engl., 34(3), 259 (1995).
2) ඵᔱᘓ᫂㸪⸨ඖ⸅㸪ࠕ᭷ᶵࣉࣟࢭࢫᏛࠖ㸪pp.51- 69 (᪥ᮏᅗ᭩, ᮾி, 1997)㸬
3) J. Shmidt, W. Hafner, R. Jira, R. Sieber, J.
Sedlmeier, A. Siebel, “The Oxidation of Olefins with Palladium Chloride Catalyst,” Angew. Chem. Int. Ed.
Engl., 1 (2), 80- 88 (1962).
4) a) K. Hori, H. Kitagawa, A. Miyoshi, T. Ohta, I.
Furukawa, “Transition Metal-Catalyzed Cyclization of 2-Allylphenol to 2,3-Dihydro-2-methylbenzofuran without ȕ-Elimination,” Chem. Lett. 1083-1084 (1998). b) T. Ohta, Y. Kataoka, A. Miyoshi, Y. Oe, I. Furukawa, Y. Ito, “Ruthenium-Catalyzed Intramolecular Cyclization of Hetero-Functionalized Allylbenzene,” J. Organomet. Chem. 692, 671-677 (2007).
5) Y. Ito, R. Kato, K. Hamashima, Y. Kataoka, Y. Oe,
T. Ohta, I. Furukawa, “Intramolecular Cyclization of Phenol Derivatives with C=C Double Bond in a Chain,” J. Organomet. Chem. 692, 691-697 (2007).
6) a) Y. Oe, T. Ohta, Y. Ito, “Ruthenium-Catalyzed Addition Reaction of Carboxylic Acids across Olefins without E-Hydride Elimination,” Chem.
Commun. 1610-1611 (2004). b) Y. Oe, T. Ohta, Y.
Ito, “Ruthenium-Catalyzed Addition Reaction of Alcohols across Olefins,” Synlett, 179-181 (2005).
7) Dppm = Bis(diphenylphosphino)methane Dppe = 1,2-Bis(diphenylphosphino)ethane Dppp = 1,3-Bis(diphenylphosphino)propane Dppb = 1,4-Bis(diphenylphosphino)butane DppBz = 1,2-Bis(diphenylphosphino)benzene
8) H. Emma, S. J. Shimpson, “Synthesis and Characterisation of [(K6-cymene)Ru(L)X2] Compounds: Single Crystal X-ray Structure of [(K6-cymene)Ru{P(OPh)3}Cl2] at 203 K,”
Polyhedron, 23 (17), 2695-2707 (2004).
9) P. E. Garrou, “'R Ring Contributions to 31P NMR Parameters of Transition-Metal-Phosphorus Chelate Complexes,” Chem. Rev. 81 (3), 229-266 (1981).
