Addition Reaction of Heteroatom Nucleophiles onto Styrene Catalyzed by Ru(II) Complex

(1)

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᰾௜ຍ཯ᛂ㸪࢜ࣞࣇ࢕ࣥ㸪࢔ࢺ࣒࢚ࢥࣀ࣑࣮

஧౯ࡢࣝࢸࢽ࣒࢘㘒యࢆ⏝࠸ࡓ࣊ࢸࣟồ᰾๣ࡢࢫࢳࣞࣥ࡬ࡢ௜ຍ཯ᛂ

኱Ụὒᖹ࣭ኴ⏣ဴ⏨࣭ఀ⸨჆ᙪ

ࡣࡌࡵ࡟

࢔ࣝࢥ࣮ࣝ㢮㸪࢚࣮ࢸࣝ㢮㸪࢚ࢫࢸࣝ㢮࠾ࡼࡧ࢔

࣑ࣥ㢮ࡣ㸪᭷ᶵྜᡂ໬Ꮫୖ㔜せ࡞ྜᡂ୰㛫యࡸ᭱⤊

⏕ᡂ≀࡜ࡋ࡚㸪ᖜᗈ࠸⏝㏵ࢆ᭷ࡍࡿ㔜せ࡞໬ྜ≀࡛

࠶ࡾ㸪ࡑࢀࡽࢆ⡆౽࠿ࡘຠ⋡ⓗ࡟ㄪ㐩ࡍࡿᡭἲࡢ㛤

Ⓨࡣ㠀ᖖ࡟㔜せ࡞ㄢ㢟࡛࠶ࡿ㸬ᚑ᮶㸪ࡇࢀࡽࡢ໬ྜ

≀ࡣ୺࡜ࡋ࡚ồ᰾ⓗ⨨᥮཯ᛂ࡟ࡼࡗ࡚ྜᡂࡉࢀ࡚

ࡁࡓࡀ㸪ᑡ࡞ࡃ࡜ࡶ┠ⓗࡢ໬ྜ≀࡜➼ࣔࣝ㔞ࡢᗫᲠ

≀ࡀ๪⏕ࡋ࡚ࡋࡲ࠺ࡓࡵ㸪ࡑࢀࡽ࡟ྲྀࡗ࡚᭰ࢃࡿᡭ ἲࡢ㛤Ⓨࡀồࡵࡽࢀࡿ¹⁾㸬࢜ࣞࣇ࢕ࣥ㢮ࡣ▼Ἔ㈨※

ࡢ➨୍ḟ୰㛫ཎᩱ࡜ࡋ࡚㇏ᐩ࡟ᚓࡽࢀ㸪⌧௦࡛ࡶ▼

Ἔ໬Ꮫᕤᴗࡢ୰᰾ࢆᢸ࠺ධᡭᐜ᫆࡞ྜᡂཎᩱࡢ୍

ࡘ࡛࠶ࡿ ²⁾㸬ࡑࡢࡼ࠺࡞࢜ࣞࣇ࢕ࣥ㢮࠿ࡽࡢ࢔ࣝࢥ

࣮ࣝ㢮㸪࢚࣮ࢸࣝ㢮㸪࢚ࢫࢸࣝ㢮࠾ࡼࡧ࢔࣑ࣥ㢮ࡢ

ྜᡂἲࡣ㸪ᙉ㓟ࢆゐ፹࡜ࡍࡿồ᰾๣ࡢ௜ຍ཯ᛂࡀ▱

ࡽࢀ࡚࠸ࡿ㸬ࡇࡢ཯ᛂ࡛ࡣ㸪௜ຍ࡜࠸࠺཯ᛂᙧᘧ࠿

ࡽཎᏊࡢᦆኻࡀ࡞ࡃ࢔ࢺ࣒࢚ࢥࣀ࣑࣮࡟ඃࢀ࡚࠾

ࡾ⨨᥮཯ᛂ࡟ẚ࡭࡚⎔ቃ࡟㐺ᛂࡋࡓࡶࡢ࡜ゝ࠼ࡿ㸬 ࡋ࠿ࡋ࡞ࡀࡽ㸪ゐ፹㔞࡜࠸࠼࡝ࡶᙉ㓟ࢆ⏝࠸ࡿࡓࡵ㸪 ᕤᴗ໬ࡍࡿ࡟ࡣ⎔ቃࡸタഛ࡬ࡢ㈇Ⲵࡀၥ㢟࡛࠶ࡿ㸬

୍᪉㸪㑄⛣㔠ᒓ㘒యࢆ⏝࠸ࡓᆒ୍⣔ゐ፹཯ᛂࡣ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: yoe@mail.doshisha.ac.jp Tetsuo OHTA; Telephone: +81-774-65-6548, FAX: +81-774-65-6789, E-mail: tota@mail.doshisha.ac.jp

** Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University

(2)

ከᵝ࡞཯ᛂࢆไᚚ࡛ࡁࡿ࡜࠸ࡗࡓⅬ࡛㸪⌧ᅾ᭱ࡶά

Ⓨ࡟◊✲ࡉࢀ࡚࠸ࡿศ㔝ࡢ୍ࡘ࡛࠶ࡿ㸬㑄⛣㔠ᒓ㘒 యࢆ⏝࠸ࡓ࣊ࢸࣟồ᰾๣࡜࢜ࣞࣇ࢕ࣥࡢ཯ᛂ࡜ࡋ

࡚Wacker཯ᛂࡀᣲࡆࡽࢀࡿࡀ㸪EỈ⣲⬺㞳ࢆ㉳ࡇ

ࡍࡇ࡜࠿ࡽ༢⣧࡞௜ຍ⏕ᡂ≀ࡣᚓࡽࢀ࡞࠸³⁾㸬⿬ࢆ

㏉ࡏࡤ㸪EỈ⣲⬺㞳ࢆไᚚࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤ㸪✜

ࡸ࠿࡞᮲௳࡛ࡢ༢⣧࡞௜ຍ཯ᛂࢆ㐩ᡂ࡛ࡁࡿ㸬ࡑࡢ

ࡼ࠺࡞ほⅬ࠿ࡽ㸪ᙜ◊✲ᐊ࡛ࡣ㑄⛣㔠ᒓࡢゐ፹స⏝

ࢆ฼⏝ࡋ㸪࡞࠾࠿ࡘEỈ⣲⬺㞳ࢆไᚚࡍࡿࡇ࡜࡟ࡼ

ࡗ࡚㸪࢜ࣞࣇ࢕ࣥ࡬ࡢ࣊ࢸࣟồ᰾๣ࡢ༢⣧࡞௜ຍ཯

ᛂ࡟㛵ࡍࡿ◊✲ࢆ⥅⥆ࡋ࡚⾜ࡗ࡚ࡁࡓ㸬ࡑࡢ⤖ᯝ㸪 ศᏊෆ཯ᛂ࡛ࡣ୕౯ࡢࣝࢸࢽ࣒࢘ ^4a-b)㸪஧౯ࡢ㖡࠾

ࡼࡧ୍౯ࡢ㖟㘒య ⁵⁾ࡀ┠ⓗ࡜ࡍࡿ࢜ࣞࣇ࢕ࣥ࡬ࡢ ồ᰾๣ࡢ௜ຍ཯ᛂࢆゐ፹ࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸬≉࡟㸪

ࣝࢸࢽ࣒࢘ゐ፹ࡣࡇࡢ཯ᛂᙧᘧ࡟࠾࠸࡚၏୍୙ᩧ

཯ᛂࢆᐇ⌧ࡋࡓඃࢀࡓゐ፹⣔࡛࠶ࡿ^4b) (Scheme 1)㸬

Scheme 1. Asymmetric Intramolecular Cyclization.

ࡲࡓ㸪ศᏊ㛫཯ᛂ࡛ࡣ୕౯ࡢࣝࢸࢽ࣒࢘ゐ፹ࡀ࢝

ࣝ࣎ࣥ㓟㢮㸪࢔ࣝࢥ࣮ࣝ㢮࠾ࡼࡧࢫࣝ࣍ࣥ࢔࣑ࢻ㢮 ࡢ࢜ࣞࣇ࢕ࣥ࡬ࡢ௜ຍ཯ᛂࢆゐ፹ࡍࡿࡇ࡜ࢆぢฟ ࡋ࡚࠸ࡿ^6a-b) (Scheme 2)㸬

Scheme 2. Ru(III)-Catalyzed Intermolecular Additions.

ࡋ࠿ࡋ࡞ࡀࡽ㸪ศᏊ㛫཯ᛂ࡟࠾ࡅࡿ࢜ࣞࣇ࢕ࣥࡢ ᇶ㉁㐺⏝⠊ᅖࡣ⊃ࡃ㸪ᇶ㉁୍⯡ᛶ࡟ᐩࢇࡔゐ፹⣔ࡢ 㛤Ⓨࡀ⌧᫬Ⅼ࡟࠾࠸࡚኱ࡁ࡞ㄢ㢟࡛࠶ࡿ㸬ゐ፹άᛶ ࡢྥୖࢆᅗࡿ࡟ࡣ㸪⣔୰࡛࡝ࡢࡼ࠺࡞ゐ፹άᛶ✀ࡀ ᙧᡂࡉࢀ࡚࠸ࡿ࠿ࢆ▱ࡿࡇ࡜ࡀ᭱ࡶ㏆㐨࡟࡞ࡿࡀ㸪

୕౯ࡢࣝࢸࢽ࣒࢘㘒యࡣᖖ☢ᛶ࠾ࡼࡧ୙Ᏻᐃࡉ࠿

ࡽ㸪ࡑࢀࡽࢆྠᐃࡍࡿࡇ࡜ࡣ㠀ᖖ࡟ᅔ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ࡀᚓࡽࢀࡓࡢ࡛௨ୗ࡟ሗ࿌ࡍࡿ㸬

ヨ⸆࠾ࡼࡧᐇ㦂᪉ἲ ヨ⸆

ᇶ㉁ࡢࢫࢳࣞࣥ㸪N࣓ࢳࣝࢺࢩࣝ࢔࣑ࢻ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ሷ໬࣓ࢳࣞࣥ㸪

࠾ࡼࡧ㔜ࢡ࣒ࣟࣟ࣍ࣝ㸪࣊࢟ࢧࣥࡣỈ⣲໬࢝ࣝࢩ࢘

࣒࡟࡚⬺Ỉᚋ㸪࢔ࣝࢦࣥẼὶୗ࡟࡚ᖖᅽ⵨␃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

ࣇ࣮࣒ࣞࢻࣛ࢖ᚋ㸪࢔ࣝࢦࣥࢆ඘ሸࡋࡓ୕ཱྀ཯ᛂ 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⁐

(3)

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┿✵ୗ࡛஝

⇱ࡍࡿࡇ࡜࡟ࡼࡗ࡚㸪┠ⓗ࡜ࡍࡿ㘒యࡀᚓࡽࢀࡓ㸬 ᚓࡽࢀࡓ㘒యࡣ≉࡟⢭〇ࡍࡿࡇ࡜࡞ࡃ㸪ࡑࡢࡲࡲḟ ࡢ཯ᛂ࡟౑⏝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

ࣇ࣮࣒ࣞࢻࣛ࢖ᚋ㸪࢔ࣝࢦࣥࢆ඘ሸࡋࡓ୕ཱྀ཯ᛂ 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࢔

ࣝࢦࣥୗ࡛ࢭࣛ࢖ࢺࣃࢵࢻࢆ㏻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┿✵ୗ࡛

஝⇱ࡍࡿࡇ࡜࡟ࡼࡗ࡚㸪┠ⓗ࡜ࡍࡿ㘒యࡀᚓࡽࢀࡓ㸬 X⥺⤖ᬗᵓ㐀ゎᯒ⏝ࡢ༢⤖ᬗࡣ㸪ࢡ࣒ࣟࣟ࣍ࣝ࡜

࣊࢟ࢧࣥ࠿ࡽᚓࡓ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᰾๣ࡢ௜ຍ཯ᛂ

඾ᆺ౛࡜ࡋ࡚㸪N-࣓ࢳࣝࢺࢩࣝ࢔࣑ࢻ࡜ࢫࢳࣞࣥࡢ

཯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-࣓ࢳࣝࢺࢩࣝ࢔࣑ࢻ (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

௨๓ࡼࡾ஧౯ࡢࣝࢸࢽ࣒࢘ゐ፹ࢆ⏝࠸ࡓ᳨ウࢆ

⾜ࡗ࡚ࡁࡓࡀ㸪࠸࠿࡞ࡿሙྜ࡟࠾࠸࡚ࡶ஧౯ࡢࣝࢸ ࢽ࣒࢘㘒యࡶゐ፹๓㥑య࡜ࡋ࡚᭷ຠ࡟ࡣാ࠿࡞࠿

ࡗࡓ㸬ᡃࠎࡣ㸪ࡇࡢせᅉࢆ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒 య࡟ࡋࡓ㝿ࡢⰾ㤶᪘⁐፹࡟ࡼࡿ⁐፹࿴ࡀ୙άᛶ໬

ᘬࡁ㉳ࡇࡋ࡚࠸ࡿ࡜⪃࠼ࡓ㸬ࡍ࡞ࢃࡕ㸪ⰾ㤶᪘ᛶ⁐

፹ࢆ⏝࠸ࡿ࡜㸪AgOTf࡜ࡢ࢔ࢽ࢜ࣥ஺᥮࡟ࡼࡾⓎ⏕

ࡋࡓ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒యࡀⰾ㤶᪘⣔⁐፹࡟

ࡼࡗ࡚ࢧࣥࢻ࢖ࢵࢳᆺࡢࣝࢸࣀࢭࣥ㘒య࡬࡜ኚ໬

ࡋ㸪ゐ፹࡜ࡋ࡚ࡢᶵ⬟ࢆᯝࡓࡉ࡞ࡃ࡞ࡿࡓࡵ࡛࠶ࡿ

࡜ண ࡋࡓ (Scheme 3)㸬

Scheme 3. Predicted Deactivation of Ru Catalysis by Aromatic Solvents.

ࡑࡇ࡛㸪N㸫࣓ࢳࣝࢺࢩࣝ࢔࣑ࢻ࡜ࢫࢳࣞࣥ࡜ࡢ

཯ᛂࢆࣔࢹࣝ཯ᛂ࡜ࡋ㸪ୖグࡢࡼ࠺࡞㈇ࡢຠᯝࡀ࡞

(4)

࠸࡜ண ࡉࢀࡿࢡ࣒ࣟࣟ࣍ࣝࢆ⁐፹࡜ࡋ࡚㸪㘒యࡢ

⁐ゎᗘ࠾ࡼࡧᏳᐃᛶࢆᮇᚅࡋ࡚ࢸࢺࣛࢡࣟࣟࣅࢫ(p 㸫ࢩ࣓ࣥ)ࢪࣝࢸࢽ࣒࢘㘒య [(p-cymene)RuCl2]2 ࢆ ゐ፹๓㥑య࡜ࡋ࡚㑅ᐃࡋ㸪཯ᛂ᮲௳ࡢ᳨ウࢆ⾜ࡗࡓ㸬 ࡑࡢ⤖ᯝࢆ㸪Table 1࡟♧ࡍ㸬

Table 1. Optimization of Reaction Conditions^a

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 1࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟㸪ண᝿ࡋࡓ㏻ࡾ࡟஧౯

ࡢࣝࢸࢽ࣒࢘㘒య࡛ࡶ⁐፹࡟ࡼࡗ࡚ゐ፹ࡀኻάࡉ

ࢀ࡞ࡅࢀࡤ㸪ప཰⋡࡞ࡀࡽࡶ཯ᛂࡣ᭷ព࡟㐍⾜ࡍࡿ

(Entry 1)㸬ࡉࡽ࡟㸪㓄఩Ꮚࢆ஧ᗙࡢ࣍ࢫࣇ࢕ࣥ㓄఩

Ꮚ࡜ࡍࡿࡇ࡜࡛㸪80%௨ୖࡢ㧗཰⋡࡛┠ⓗ≀ࡀᚓࡽ

ࢀࡓ (Entries 2-6)㸬ࡇࢀࡽࡢ⤖ᯝࡣ㸪༢ᗙ㓄఩Ꮚࡢ ࢺࣜࣇ࢙ࢽࣝ࣍ࢫࣇ࢕ࣥ (PPh₃) ࢆ⏝࠸ࡓሙྜ, ཯ ᛂ୰࡟ࣝࢸࢽ࣒࢘࠿ࡽࡢ㓄఩Ꮚࡢゎ㞳ࡀ㉳ࡇࡾ㸪ᇶ

㉁࡛࠶ࡿࢫࢳࣞࣥࡢⰾ㤶⎔ࡀ㸪ⰾ㤶᪘⣔ࡢ⁐፹࡜ྠ

ᵝࡢゐ፹ኻάຠᯝࢆࡶࡓࡽࡋࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼

ࡽࢀࡿ㸬Table 1ࡢ⤖ᯝࡼࡾ㸪஧౯ࡢࣝࢸࢽ࣒࢘ゐ፹

⣔ࡶ୕౯ࡢࣝࢸࢽ࣒࢘ゐ፹⣔࡜ྠ➼㸪࠶ࡿ࠸ࡣࡑࢀ

௨ୖࡢゐ፹άᛶࢆ᭷ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ㸬 ḟ࡟㸪ᡃࠎࡣ⣔୰࡟Ⓨ⏕ࡋ࡚࠸ࡿゐ፹άᛶ✀ࡢゎ

᫂࡟ྲྀࡾ⤌ࢇࡔ㸬௒ᅇࡢゐ፹཯ᛂ࡛ࡣ㸪཯ᛂࡢ๓ẁ 㝵࡜ࡋ࡚[(p-cymene)RuCl2]2࡟AgOTf 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]2࡟ࢺࣜࣇࣝ࢜

࣓ࣟࢱࣥࢫࣝ࣍ࣥ㓟㖟 (AgOTf) ࢆ㔜ࢡ࣒ࣟࣟ࣍ࣝ

୰࡟࡚ 3 ᫬㛫཯ᛂࡉࡏࡓᚋ㸪DppBz ࢆస⏝ࡉࡏ㸪 NMRゎᯒࢆ⾜ࡗࡓ㸬Table 2࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟㸪

AgOTf ࡟ࡼࡗ࡚ฎ⌮ࡍࡿࡇ࡜࡟ࡼࡾ㸪 p-ࢩ࣓ࣥ⎔

ୖࡢࣉࣟࢺࣥࡀ᫂ࡽ࠿࡟ప☢ሙࢩࣇࢺࡋ࡚࠸ࡿࡇ

࡜㸪[(p-cymene)RuCl₂]2 ⏤᮶ࡢࢩࢢࢼࣝࡀほ ࡉࢀ

࡞ ࠸ ࡇ ࡜ ࡀ ¹H NMR ࠿ ࡽ ☜ ㄆ ࡉ ࢀ 㸪 [(p-cymene)RuCl2]2ࡣูࡢ㘒య࡬࡜ኚ໬ࡋ࡚࠸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ࡢ໬Ꮫࢩࣇ

ࢺ್ (26 ppm) ࡟ẚ࡭࡚኱ࡁࡃప☢ሙࢩࣇࢺࡋ࡚࠸

ࡿࡓࡵ㸪DppBzࢆ⏝࠸ࡓ㘒యࡣ஧ࡘࡢࣜࣥཎᏊ࡜ࣝ

ࢸࢽ࣒࢘ࢆྵࡴ஬ဨ⎔ᵓ㐀ࢆྲྀࡗ࡚࠸ࡿࡇ࡜ࡀ♧

၀ࡉࢀࡿ⁹⁾㸬ࡉࡽ࡟㸪¹⁹F NMR࡟࠾࠸࡚㸪-78.4 ppm, -78.5 ppm࡟࡯ࡰ1 : 1ࡢ✚ศẚ࡛஧ᮏࡢࢩࣥࢢࣞࢵ

ࢺࡀ☜ㄆ࡛ࡁࡓ㸬ࡇࡢࡇ࡜࠿ࡽ㸪୍ࡘࡢOTfࡣࣝࢸ ࢽ࣒࢘࡟㓄఩ࡋ࡚࠾ࡾ㸪ࡶ࠺୍᪉ࡢOTfࡣ࢝࢘ࣥࢱ

࣮࢔ࢽ࢜ࣥ࡜ࡋ࡚Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀ♧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࠸ࡿࡇ࡜ࡀண᝿ࡉࢀࡿ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

(5)

FAB-MSࢫ࣌ࢡࢺ࡛ࣝࡢゎᯒࡣࡑࡢண᝿ࢆ⿬௜ࡅ

ࡿࡶࡢ࡜࡞ࡾ㸪[(p-cymene)Ru(OTf)(DppBz)]⁺ࡢࣇࣛ

ࢢ࣓ࣥࢺ࢖࢜ࣥࣆ࣮ࢡࡢ831 m/z ࡀ☜ㄆࡉࢀࡓ㸬୍

᪉㸪୙⣧≀࡜ࡋ࡚AgX (X = OTf or Cl) ࡜DppBzࡢ 1 : 2㘒య࡜⪃࠼ࡽࢀࡿ Ag(DppBz)⁺ࡢศᏊ࢖࢜ࣥࣆ

࣮ࢡ (1001 m/z)ࡶ☜ㄆࡉࢀࡓ㸬

௨ୖ, NMR࠾ࡼࡧMSࢫ࣌ࢡࢺࣝ࡟ࡼࡿゎᯒ࠿ࡽ

⪃ ࠼ 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 ࡜ DppBzࢆ཯ᛂࡉࡏ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㦂࡛ᚓࡽࢀࡓ್࡜ࡼࡃ

୍⮴ࡋࡓ㸬ࡲࡓ㸪ᖾ࠸࡟ࡶᚓࡽࢀࡓ㘒యࡢ༢⤖ᬗࢆ

ࢡ࣒ࣟࣟ࣍ࣝ/࣊࢟ࢧࣥ࠿ࡽࡢ෌⤖ᬗ࡟ࡼࡗ࡚ㄪ〇 ࡍࡿࡇ࡜ࡀ࡛ࡁ㸪X⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡗ࡚ࣝࢸࢽ

࣒࢘࡬ࡢྛ㓄఩Ꮚࡢ㓄఩ᙧᘧࡣࢫ࣌ࢡࢺࣝゎᯒ࠿

ࡽண᝿ࡋࡓࡶࡢ࡟୍⮴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.

࣑ࢻ࡜ࢫࢳࣞࣥࡢ཯ᛂࢆ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ࡑࡢࡀ࢜ࣞࣇ࢕ࣥ࡬ࡢ࣊ࢸࣟồ᰾๣ࡢ࢜ࣞࣇ࢕

ࣥ࡬ࡢ௜ຍ཯ᛂࢆ㐍⾜ࡉࡏ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ

ࡶࡢ࡛࠶ࡿ㸬

(6)

㸲㸬⤖ㄽ

ᡃࠎࡣ㸪஧౯ࡢ࢝ࢳ࢜ࣥᛶࣝࢸࢽ࣒࢘㘒యࡀ࣊ࢸ

ࣟồ᰾๣ࡢ࢜ࣞࣇ࢕ࣥ࡬ࡢ௜ຍ཯ᛂ࡟ᑐࡍࡿゐ፹ άᛶࢆ᭷ࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸬ࡑࡢ୰࡛㸪වࡡ࡚࠿

ࡽࡢᠱ᱌࡛࠶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ࡇࡢሙࢆ೉ࡾ࡚㸪῝ࡃឤ ㅰࡢពࢆ⾲ࡋ㸪ᚚෞ⚟ࢆ࠾♳ࡾࡍࡿ࡜࡜ࡶ࡟㸪ྠᩍ

ᤵ࡟ᮏㄽᩥࢆᤝࡆࡿ㸬

ᮏ◊✲ࡢ୍㒊ࡣ㸪ࠕ⌮ᕤᏛ◊✲ᡤ 2008 ᖺᗘྠᚿ

♫኱Ꮫ⌮ᕤᏛ◊✲ᡤ◊✲ຓᡂ㔠 (ಶே)ࠖࡢᨭ᥼ࢆཷ

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᭷ᶵࣉࣟࢭࢫ໬Ꮫࠖ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).