Copper-Catalyzed Addition Reaction of Carbon Nucleophiles to Olefins
Kei NIIGAWA, Noriko OHNISHI, Takashi MIYAMOTO, Tetsuo OHTA,* and Yoshihiko ITO**
(Received October 1, 2007)
Addition reaction of carbon nucleophiles to olefins was studied using copper as a catalyst. For example, reaction of dibenzoylmethane (2a) with styrene (1a) in the presence of Cu(OTf)2 catalyst at 70 oC for 24 h in benzene gave 1,3-diphenyl-2-(1-phenylethyl)propane-1,3-dione (3aa) in 95% yield. This reaction was able to be applied for various E-dicarbonyl compounds and olefins including diene. Furthermore, reaction mechanism was proposed.
-G[YQTFU : carbon nucleophile, olefin, copper, keto-enol tautomerism 䉨䊷䊪䊷䊄 : ⚛᳞ᩭ, ࠝࡈࠖࡦ, ㌃, ࠤ࠻㧙ࠛࡁ࡞ᄌ⇣ᕈ
㌃⸅ᇦࠍ↪ߚ⚛᳞ᩭߩࠝࡈࠖࡦ߳ߩઃടᔕ
ᣂᎹ ᘮᄢ ♿ሶችᧄ ፏผᄥ↰ ື↵દ⮮ ཅᒾ
㧝 ߪߓߦ
ࠝࡈࠖࡦ㘃ߩቭ⢻ၮൻߩᚻᴺߩ৻ߟߦㆫ⒖㊄ ዻ⸅ᇦࠍ↪ߚ᳞ᩭߩ⸅ᇦ⊛ઃടᔕ߇ࠆ 1)㧚
ࠝࡈࠖࡦ㘃ߣ᳞ᩭߣ߁Ყセ⊛ଔߢᚻኈ ᤃߥ⊒ේᢱߩ⚵ߺวࠊߖ߆ࠄ㧘ઃടଔ୯ߩ㜞ࠕ
࡞ࠦ࡞߿ࠕࡒࡦ㧘ࠛࠬ࠹࡞ߥߤߩ⺃ዉ߇ᓧࠄࠇ ࠆߚߦ㧘㕖Ᏹߦ↪ߥᔕߢࠆߣ߃ࠆ㧚߹ߚ㧘
ઃടߣ߁ᔕᒻᑼ߆ࠄࡠࠬߩߥࠕ࠻ࡓࠛࠦࡁ ࡒߥᔕߩታ߇ᦼᓙߢ߈ࠆߚㄭᐕᄢᄌᵈ⋡
R' + Nu-H
R' H
Nu or
R' Nu
H
Markovnikov anti-Markovnikov Nu = OH, OR, COOR, NR2, etc.
Scheme 1
ࠍᶎ߮㧘ᵴ⊒ߦ⎇ⓥ߇ⴕࠊࠇߡࠆ㧚ߒ߆ߒ㧘ߎࠇ
߹ߢߩ⎇ⓥߪ㧘⓸⚛߿㉄⚛ߥߤߩࡋ࠹ࡠේሶࠍ
ߔࠆ᳞ᩭࠍ↪ߚ⸅ᇦ⊛ઃടᔕ߇߶ߣࠎߤߢ
ߞߚ㧔Scheme 1㧕㧚
৻ᣇ㧘Ǫ㧙ࠫࠤ࠻ࡦ㘃߿ࡑࡠࡦ㉄⺃ዉߦઍߐ ࠇࠆᵴᕈࡔ࠴ࡦൻว‛ߪ⚛᳞ᩭߣߒߡᯏ⢻
ߒᓧࠆߦ߽߆߆ࠊࠄߕ㧘ࠝࡈࠖࡦ㘃߳ߩ⸅ᇦ⊛ઃ
ടᔕߩ⹜ߺߪߏߊᦨㄭ߹ߢⴕࠊࠇߡߥ߆ߞߚ㧚
ᓥ᧪ߩ 1,3-ࠫࠞ࡞ࡏ࠾࡞ൻว‛ߩࠕ࡞ࠠ࡞ൻᔕ
ߢߪේᢱၮ⾰ߦኻߒߡᒰ㊂એߩႮၮ⹜⮎ߣࡂࡠ ࠕ࡞ࠞࡦࠍᔅⷐߣߔࠆ߇㧘ࠝࡈࠖࡦ߳ߩઃടᔕ ߇ㅴⴕߔࠇ߫㧘ߪࠆ߆ߦή㚝ߩߥวᚑᔕ߇㆐ᚑ ߢ߈ࠆޕ߹ߚ㧘Ⴎၮࠍᔅⷐߣߒߥߣ߁᷷ߥ᧦
ઙߢᔕ߇ㅴⴕߔࠇ߫㧘Ⴎၮߦਇቯߥቭ⢻ၮࠍ߽
ߟൻว‛ߩวᚑ߽㆐ᚑߢ߈ࠆߣ߁ὐ߽ࠆ 㧔Scheme 2㧕㧚
* Department of Molecular Science and Technology, Doshisha University, Kyotanabe, Kyoto 610-0321 Telephone: +81-774-65-6548, Fax: +81-774-65-6789, E-mail: [email protected]
** రหᔒ␠ᄢቇቴຬᢎ 2006ᐕ1223ᣣㅤ
ߏߊᦨㄭ1,3-ࠫࠤ࠻ࡦ㘃ࠍ⚛᳞ᩭߣߔࠆࠝ
ࡈࠖࡦ㘃߳ߩ⸅ᇦ⊛ઃടᔕ߇ႎ๔ߐࠇߚ߇㧘ߘࠇ ࠄߩႎ๔ߢߪ㜞ଔߥAuCl3߿㧘Ḩ᳇ߦᢅᗵߢขࠅ ᛒߦߊ AgOTf ࠍᔅⷐߣߒ㧘ታ↪ᕈߦ߆ߌࠆ߽
ߩߢߞߚ2)㧚
R R
O O
1) Base 2)
cat.
R'
R R
O O
R
O O
R' R
+ X- X
R'
R'
Scheme 2
ߘߎߢᧄ⎇ⓥߢߪ㧘ࠃࠅታ↪⊛ߥᔕࡊࡠࠬߩ 㐿⊒ࠍ⋡ᜰߒ㧘ଔߢ߆ߟขࠅᛒ߇ኈᤃߥCu⸅ ᇦߦ⌕⋡ߒߚ㧚ࡑࠗࠤ࡞ઃടᔕࠍߪߓ㧘⒳ޘߩ
ᔕߦ߅ߡ㧘࡞ࠗࠬ㉄⸅ᇦߣߒߡ㌃Ⴎߪᐢߊ↪
ࠄࠇߡ߅ࠅ㧘⚛᳞ᩭߩࠝࡈࠖࡦ㘃߳ߩ⸅ᇦ⊛
ઃടᔕߦㆡ↪ߢ߈ࠆ߆ᬌ⸛ࠍⴕߞߚ㧚
㧞 ታ㛎ᣇᴺ ಽᨆᯏེ
ࡈࠛᄌ឵ᩭ⏛᳇㡆ⵝ⟎㧦(FT-NMR) Varian
Mercury plus 300-4N㧚ࠟࠬࠢࡠࡑ࠻ࠣࡈࠖ⾰
㊂ಽᨆ⸘ (GC-MS)㧦ፉᵤᚲGC17A/QP-5000 system㧚⾰㊂ಽᨆ(FAB-MS)㧦ᣣᧄ㔚ሶ JMS-700㧚
⭯ጀࠢࡠࡑ࠻ࠣࡈࠖ↪ࠪࠞࠥ࡞ࡊ࠻
(TLC)㧦Merck␠ ࠪࠞࠥ࡞60 ࡊ࠻F254㧚
ᔕ⹜ߩ⺞
ṁᇦߪᏒ⽼ຠࠍᏱᴺ3㧕ߦࠃࠅ⣕᳓ᓟ⫳⇐ߒ㧘⫳⇐
ᓟࠕ࡞ࠧࡦࠟࠬࠍ10ಽ㑆ࡃࡉ࡞ߐߖࠆᣇᴺߢ⣕᳇
ࠍⴕ㧘ࠕ࡞ࠧࡦ㔓࿐᳇ਅߢሽߒߚ߽ߩࠍ↪ߚ㧚 Ꮢ⽼ߩ⹜⮎ߪߘߩ߹߹♖ߔࠆߎߣߥߊ↪ߒߚ㧚
㌃⸅ᇦࠍ↪ߚ⚛᳞ᩭߣࠝࡈࠖࡦߣߩ
ઃടᔕ
80 mLࠪࡘࡦࠢ▤ࠍࡈࡓ࠼ࠗ㧘ࠕ࡞ࠧࡦ
⟎឵ߒߚᓟ㧘Cu(OTf)2 (0.0181 g, 0.05 mmol)㧘⚛᳞
ᩭ (1 mmol) ࠍട߃㧘ṁᇦ2 mL߅ࠃ߮ࠝࡈࠖ
ࡦ (2 mmol) ࠍട߃ߡ㧘70 ͠ߢ24ᤨ㑆ᠣᜈߒߚ㧚
ᔕ⚳ੌᓟ㧘ࠫࠛ࠴࡞ࠛ࠹࡞ߢᏗ㉼ߒ㧘⫳⇐᳓ߢ 3࿁㧘㘻㘩Ⴎ᳓ߢ1࿁ᵞᵺߒ㧘⎫㉄࠽࠻࠙ࡓࠍ ട߃ߡੇ῎ߐߖߚ㧚Ớ❗ᓟ㧘ࠪࠞࠥ࡞ࠢࡠࡑ࠻ࠣ
ࡈࠖߢන㔌♖ߒߚ㧚↢ᚑ‛ߪ1H-NMR㧘߮
GC-MS㧘FAB-MSߦࠃࠅหቯࠍⴕߞߚ㧚
1,3-Diphenyl-2-(1-phenylethyl)propane-1,3- dione (3aa)
1H NMR (300 MHz, CDCl3)G8.03 (2H, d, J = 7.2 Hz), 7.73 (2H, d, J = 7.2 Hz), 7.58-7.04 (11H, m), 5.59 (1H, d, J = 10.2 Hz), 4.07 (1H, m), 1.34 (3H, d, J = 6.9 Hz).
FAB-MS (m/z) 328.
2-(1-Phenylethyl)-1,3-phenylbutane-1,3-dione (3ab)
1H NMR (300 MHz, CDCl3)G8.10 (1H, d, J = 10.2 Hz), 7.79 (1H, d, J = 10.2 Hz), 7.62-7.03 (7H, m), 4.86 (1H, d, J = 10.2 Hz), 3.90-3.82 (1H, m), 1.90 (3H, s, J = 6.9 Hz), 1.30 (3H, d, J = 6.6 Hz).
GC-MS (m/z) 266.
3-(1-Phenylethyl)pentane-2,4-dione (3ac)
1H NMR (300 MHz, CDCl3)G7.29-7.15 (5H, ѽҏm), 4.05 (1H, d, J = 11.2 Hz), 3.60 (1H, m), 2.26 (3H, s), 1.83 (3H, s), 1.21 (3H, d, J = 7.2 Hz).
GC-MS (m/z) 204.
3-(1-Phenylethyl)heptane-3,5-dione (3ad)
1H NMR (300 MHz, CDCl3)G7.29-7.14 (5H, ѽҏm), 4.03 (1H, d, J = 11.4 Hz), 3.68-3.58 (1H, m), 2.66-2.50 (2H, m), 2.27-2.14 (1H, m), 2.09-1.95 (1H, m), 1.20-1.18 (3H, d, J = 6.9 Hz), 1.09-1.04 (3H, t, J = 7.2 Hz), 0.72-0.67 (3H, t, J = 7.2 Hz).
GC-MS (m/z) 232.
2-Acethyl-2-(1-phenylethyl)cyclopentanone (3ae)
1H NMR (300 MHz, CDCl3)G7.29-7.26 (5H, ѽҏm), 3.79 (1H, m), 2.77-2.67 (1H, m), 2.38 (3H, s), 2.20-2.01 (1H, m), 2.20-2.10 (2H, m), 2.08-1.70 (5H, m), 1.19 (3H, d, J
= 7.2 Hz).
GC-MS (m/z) 230.
D-Acethyl-E-methyl methyl benzenepropanoate (3af)
1H NMR (300 MHz, CDCl3)G(5H, m), 3.82-3.74 (1H, m), 3.57-3.51 (1H, m), 3.42, 3.75 (3H, s), 2.29, 1.91 (3H, s), 1.29, 1.24 (3H, d, J = 6.9 Hz).
GC-MS (m/z) 220.
2-(1-(4-Chlorophenyl)ethyl)-1,3-diphenyl- propane-1,3-dione (3ba)
1H NMR (300 MHz, CDCl3)G8.04 (2H, d, J = 8.0 Hz), 7.75 (2H, d, J = 8.0 Hz), 7.58-7.12 (10H, m), 5.57 (1H, d, J = 10.2), 4.07 (1H,m), 1.32 (3H, d, J = 6.9 Hz).
FAB-MS (m/z) 363.
2-(1-(4-Methylphenyl)ethyl)-1,3-diphenyl- propane-1,3-dione (3ca)
1H NMR (300 MHz, CDCl3)G8.04 (2H, d, J = 8.0 Hz), 7.75 (2H, d, J = 8.0 Hz), 7.58-7.12 (10H, m), 5.57 (1H, d, J = 10.2), 4.07 (1H,m), 2.21 (3H, s), 1.32 (3H, d, J = 6.9 Hz).
FAB-MS (m/z) 342.
2-(Bicyclo[2.2.1]heptan-2-yl)-1,3-diphenyl- propane-1,3-dione (3ea)
1H NMR (300 MHz, CDCl3)G8.03 (2H, d, J = 7.2 Hz), 7.93 (2H, d, J = 6.8 Hz), 7.57-7.37 (6H, m), 5.03 (1H, d, J = 10.8), 2.74 (1H, m), 2.24 (1H, m), 1.96 (1H, s), 1.62 (1H, m), 1.51-1.48 (3H, m) , 1.30 (1H, m), 1.22-1.19 (2H, m), 1.13-1.10 (1H, m).
FAB-MS (m/z) 318.
2-(Cyclohex-2-enyl)-1,3-diphenyl-propane- 1,3-dione (3fa)
1H NMR (300 MHz, CDCl3)G7.99-7.97 (4H, m),
7.55-7.50 (2H, m), 7.43-7.34 (4H, m), 5.75-5.68 (1H, m), 5.52-5.48 (1H, m), 5.30 (1H, d, J = 9.9 Hz), 3.52-3.44 (1H, m), 2.03-2.00 (2H, m), 1.81-1.66 (2H, m), 1.63-1.25 (2H, m).
GC-MS (m/z) 304.
㧟㧚 ⚿ᨐߣ⠨ኤ
ࠫࡌࡦ࠱ࠗ࡞ࡔ࠲ࡦߩࠬ࠴ࡦ߳ߩઃടᔕ ߦ߅ߌࠆ㌃Ⴎߩ⸅ᇦ↪
Cu-Catalyst (10 mol%) CHCl3, 70 oC, 24 h
Ph Ph
O O
Ph O
Ph O +
1a 2a
3aa
Scheme 3
߹ߕ㧘ࠬ࠴ࡦ (1a) ߣࠫࡌࡦ࠱ࠗ࡞ࡔ࠲ࡦ (2a) ߣߩᔕࠍࡕ࠺࡞ᔕߣߒ㧘㌃Ⴎߩ⸅ᇦ↪ߩᬌ⸛
ࠍⴕߞߚ㧔Scheme 3㧕㧚ߘߩ⚿ᨐࠍTable 1ߦ␜ߒߚ㧚 Cu(OTf)2ࠍ⸅ᇦߣߒߚߣ߈㧘86 %₸ߢ⋡⊛ߣߔ ࠆઃട3aaࠍᓧߚ߇㧘↢ᚑ‛ߣߒߡࠬ࠴ࡦߩ
ੑ㊂߇න㔌ߐࠇߚ (Entry 1)㧚Cu(OAc)2㧘Cu(acac)2
ࠍ⸅ᇦߣߒߡ↪ߚߣߎࠈ㧘⋡⊛‛ߪ߶ߣࠎߤᓧࠄ ࠇߥ߆ߞߚ㧔Entries 2 and 3㧕㧚߹ߚCu(OTf)2ߣห᭽
ߦᒝ㉄ߩᓎႮၮࠍࠕ࠾ࠝࡦߣߔࠆ㌃Ⴎߢࠅ㧘2- ࠕ࡞ࡈࠚࡁ࡞ߩಽሶౝⅣൻᔕ4)ߦ߅ߡᔕ
Table 1. Effect of copper-catalysta)
Entry Cu catalyst Yield (%)b)
1 Cu(OTf)2 86
2 Cu(OAc)2 Trace
3 Cu(acac)2 Trace
4 Cu(ClO4)2㨯6H2O 72 5 Cu(BF4)2㨯6H2O N.r.
6 Cu(CH3CN)4PF6 N.r.
a) Styrene (2.0 mmol), Dibenzoylmethane (1.0 mmol), Cu-catalyst (0.10 mmol), CHCl3 (2 mL), at 70 oC, for 24 h, under Ar.
b) Isolated yield.
ᵴᕈࠍ␜ߒߚ Cu(ClO4)2㨯6H2O ࠍ⸅ᇦߣߒߡ↪
ߚ႐ว߽㜞₸ߢ3aaࠍᓧߚ㧔Entry 4㧕㧚ߒ߆ߒ㧘 ᒝ㉄ߩᓎႮၮࠍࠕ࠾ࠝࡦߦ߽ߟ߇ಽሶౝⅣൻ
ᔕߦᵴᕈࠍ␜ߐߥ߆ߞߚCu(BF4)2㨯6H2Oࠍ⸅ᇦߣ ߒߡ↪ߚ႐ว㧘ᔕߪోߊㅴⴕߖߕ㧘ࠬ࠴ࡦ ߩ ੑ ㊂ ൻ ߽ ߎ ࠄ ߥ ߆ ߞ ߚ (Entry 5)㧚 Cu(CH3CN)4PF6ߢ߽ᔕߪㅴⴕߒߥ߆ߞߚ㧔Entry 6㧕㧚
㌃Ⴎߩ⸅ᇦ㊂ߩᬌ⸛
ᦨ߽ᵴᕈߩ㜞 Cu(OTf)2ࠍ↪ߡ⸅ᇦ㊂ߩᬌ⸛
ࠍⴕߞߚ㧔Scheme 4㧕㧚ߘߩ⚿ᨐࠍTable 2ߦ␜ߒߚ㧚
⸅ᇦ㊂ߣߒߡߪ㧘⚛᳞ᩭߦኻߒߡ 5.0 mol%
߅ࠃ߮2.5 mol%ߦᷫࠄߒߚ᧦ઙߢ߽㧘චಽߦ⸅ᇦᵴ ᕈࠍ␜ߔߎߣ߇ಽ߆ߞߚ (Entries 2 and 3)㧚
Ph Ph
O O
Ph O
Ph O Cu(OTf)2
CHCl3, 70 oC, 24 h +
1a 2a
3aa
Scheme 4
Table 2. Effect of amount of catalysta)
Entry Amount of catalyst (mol%) Yield (%)b)
1 2.5 87
2 5.0 90
3 10 86
a) Styrene (2.0 mmol), Dibenzoylmethane (1.0 mmol), Cu(OTf)2, CHCl3 (2 mL), at 70 oC, for 24 h, under Ar. b) Isolated yield.
ṁᇦലᨐ
వ߶ߤߩᬌ⸛ߦ߅ߡᦨ߽⦟₸ࠍਈ߃ߚ᧦
ઙ㧘Cu(OTf)2 5.0 mol%ߢṁᇦലᨐߩᬌ⸛ࠍⴕߞߚ 㧔Scheme 5㧕㧚ߘߩ⚿ᨐࠍTable 3ߦ␜ߒߚ㧚
ࡌࡦࡦ㧘࠻࡞ࠛࡦߥߤߩήᭂᕈṁᇦߢ߽ࠢࡠࡠ ࡎ࡞ࡓṁᇦਛߣห╬ߩ₸ߢ⋡⊛ߣߔࠆઃട
3aaࠍᓧߚ (Entry 1 vs. 3)㧚㈩ᕈṁᇦߢࠆ࠹࠻
ࡅ࠼ࡠࡈࡦ㧘ࠕ࠻࠾࠻࡞ࠍṁᇦߣߒߚ႐ว㧘
₸ߪૐߊߥߞߚ (Entries 4 and 5)㧚ߎࠇߪ㧘ߎࠇ ࠄߩṁᇦ߇㌃ߦ㈩ߒߡ㈩㍲ߣߥࠅ㧘ቯൻߐ ࠇ⸅ᇦᵴᕈ߇ૐਅߔࠆ߆ࠄߢࠆߣ⠨߃ࠄࠇࠆ㧚ࠛ
࠲ࡁ࡞ࠍ↪ߚ႐ว㧘ᔕߪోߊㅴⴕߒߥ߆ߞߚ (Entry 6)㧚ࠛ࠲ࡁ࡞ߣࠫࡌࡦ࠱ࠗ࡞ࡔ࠲ࡦߣߩ᳓
⚛⚿วᒻᚑߦࠃࠅ2aߩࠤ࠻߇ቯൻߐࠇࠆߚ㧘
ᔕ߇ㅴⴕߒߥ߆ߞߚߣ⠨߃ࠄࠇࠆ㧚
એߩߎߣ߆ࠄ㧘㕖ࡊࡠ࠻ࡦᕈߢ㧘㌃ߦኻߒߡ㈩
ജߩᒙṁᇦࠍ↪ࠆߎߣߢ㧘ᔕߪല₸ࠃߊㅴ ⴕߔࠆߣ⠨߃ࠄࠇࠆ㧚
Cu(OTf)2 (5.0 mol%) Solvent, 70 oC, 24 h
Ph Ph
O O
Ph O
Ph
1a 2a O
3aa +
Scheme 5
Table 3. Solvent effecta)
Entry Solvent Yield (%)b)
1 CHCl3 90
2 Benzene 95 3 Toluene 90 4 THF 12
5 CH3CN 16
6 EtOH N.r.
a) Styrene (2.0 mmol), Dibenzoylmethane (1.0 mmol), Cu(OTf)2 (0.05 mmol), Solvent (2 mL), at 70 oC, for 24 h, under Ar. b) Isolated yield.
㉄ߩലᨐ
ߏߊᦨㄭ㧘࠻ࡈ࡞ࠝࡠࡔ࠲ࡦࠬ࡞ࡎࡦ㉄߇ࡅ࠼
ࡠࠕࡒࡁൻᔕ߅ࠃ߮ࡅ࠼ࡠࠕ࡞ࠦࠠࠪൻᔕߩ
⸅ᇦߣߒߡ↪ߔࠆߎߣ߇ႎ๔ߐࠇߚ5)㧚หᤨߦߎ ࠇ߹ߢߦႎ๔ߐࠇߚ㊄ዻ࠻ࡈ࠻ࠍ⸅ᇦߣߔ ࠆᔕߦ߅ߡ߽⌀ߩ⸅ᇦ⒳ߪᓥ᧪⠨߃ࠄࠇߡ߈ ߚ㊄ዻ㍲ߢߪߥߊ㧘♽ਛߢ⊒↢ߒ߁ࠆTfOHߢߪ ߥ߆ߣ߁ᜰ៰߇ߥߐࠇߡߚ㧚
ߘߎߢ㧘⸅ᇦ㊂ߩ TfOH ࠍ↪ߡᔕࠍⴕߞߚ 㧔Table 4㧕㧚ߘߩ⚿ᨐ㧘⋡⊛‛ߩ₸ߪૐ߽ߩߢ
ߞߚ㧚ߎࠇߪTfOHߦࠃࠅࠬ࠴ࡦߩੑ㊂ൻ߇ㅴ ⴕߒ㧘₸ߩૐਅߦߟߥ߇ߞߚ߽ߩߣ⠨߃ࠄࠇࠆ㧚
Table 4 Effect of acid a)
Entry Acid (mol%) Yield (%)b)
1 TfOH (5 ) 23
2 TfOH (10) 14
a) Styrene (2.0 mmol), Dibenzoylmethane (1.0 mmol), TfOH, Benzene (2 mL), at 70 oC, for 24 h, under Ar. b) Isolated yield.
⚛᳞ᩭߩᬌ⸛
Cu(OTf)2 (5.0 mol%)
Benzene, 70 oC, 24 h Nu + NuH
H
1a 2a-g 3aa-af
Scheme 6
Table 5. Investigation of various Carbon Nucleophilesa)
Entry NuH Yield (%)b)
1 Ph Ph
O O
2a
95
2 Ph
O O
2b
97
3c)
O O
2c
78
4c)
O O
2d
52
5c)
O O
2e
57
6d) O
O O
2f
23
a) Styrene (1.0 mmol), Nucleophile (2.0 mmol), Cu (OTf) 2 (0.05 mmol), Benzene (2 mL), at 70 oC, for 24 h, under Ar.. b)Isolated yield
c) Nitromethane was used instead of benzene. d) Toluene was used instead of benzene at 90 oC
⚛᳞ᩭߩᬌ⸛ߣߒߡ㧘ࠫࡌࡦ࠱ࠗ࡞ࡔ࠲ࡦએ ᄖߩ᳞ᩭࠍ↪ߡᔕࠍ⹜ߺߚ㧔Scheme 6㧕㧚ߘ ߩ⚿ᨐࠍTable 5ߦ␜ߒߚ㧚
ࡌࡦ࠱ࠗ࡞ࠕ࠻ࡦ㧔2b㧕ߢߪ₸97%ߢ⋡⊛‛
ࠍᓧࠆߎߣ߇ߢ߈ߚ㧔Entry 2㧕㧚2,4-ࡍࡦ࠲ࡦࠫࠝࡦ 㧔2c㧕㧘3,5-ࡋࡊ࠲ࡦࠫࠝࡦ㧔2d㧕㧘2-ࠕ࠴࡞ࠪࠢ
ࡠࡍࡦ࠲ࡁࡦ㧔2e㧕ࠍ↪ߚߣߎࠈ㧘ࡌࡦࡦṁᇦ ߢߪ₸ߪૐ߆ߞߚ߇㧘࠾࠻ࡠࡔ࠲ࡦࠍ↪ࠆߎߣ ߢ₸ߩะ߇ࠄࠇߚ㧔Entries 3㧘4 and 5㧕㧚ၮ⾰
2dߪ2cߣᲧߴߡ┙㓚ኂ߇ᄢ߈ߚ㧘₸߇ૐ ਅߒߚߣ⠨߃ࠄࠇࠆ㧚ࠫࠤ࠻ࡦ㘃ߣᲧߴߡ㉄ᕈᐲߩ ዊߐࠕ࠻㈶㉄ࡔ࠴࡞㧔2f㧕ࠍ↪ߚߣߎࠈ㧘23%
ߣ₸ߩૐਅ߇ࠄࠇߚ㧔Entry 6㧕㧚
ࠝࡈࠖࡦၮ⾰ߩᬌ⸛
⛯ߡࠝࡈࠖࡦၮ⾰ߩᬌ⸛ࠍⴕߞߚ㧔Scheme 7㧕㧚ߘߩ⚿ᨐࠍTable 6ߦ␜ߒߚ㧚
4-ࠢࡠࡠࠬ࠴ࡦ㧔1b㧕㧘4-ࡔ࠴࡞ࠬ࠴ࡦ㧔1c㧕 ߢߪߘࠇߙࠇ₸ 90㧑㧘84㧑ߢ⋡⊛ߩઃട↢ᚑ‛
߇ᓧࠄࠇߚ㧔Entries 2 and 3㧕㧚4-ࡔ࠻ࠠࠪࠬ࠴ࡦ 㧔1d㧕ߢߪ⋡⊛‛ߪ߶ߣࠎߤᓧࠄࠇߥ߆ߞߚ㧔Entry
4㧕㧚ၮ⾰1dߪઁߩࠬ࠴ࡦ⺃ዉߣᲧセߒߡੑ㊂
ൻߩㅴⴕㅦᐲ߇ㅦߚ㧘⚛᳞ᩭߩઃടᔕ߇ ᛥߐࠇߚߩߢߪߥ߆ߣ⠨߃ࠄࠇࠆ㧚┙⊛ߥᱡ ߺࠍᜬߟߚᵴᕈߩ㜞2-ࡁ࡞ࡏ࡞ࡀࡦ㧔1e㧕ࠍ↪
ߚߣߎࠈ₸ 90%ߣ㜞₸ߢ⋡⊛‛߇ᓧࠄࠇߚ 㧔Entry 5㧕㧚1,3-ࠪࠢࡠࡋࠠࠨࠫࠛࡦ㧔1f㧕ߢߪ36%
ߩ₸ߢ⋡⊛‛߇ᓧࠄࠇߚ㧔Entry 6㧕㧚
Cu(OTf)2(5 mol%) 24 h, 70oC Benzene
R Ph Ph
O O
Ph O
Ph O
R
1a-g 2a
3aa-fa +
Scheme 7
Table 6. Investigation of various Olefinsa)
Entry Olefin Yield (%)b) 1
1a
95
2 Cl
1b
90
3
1c
84
4 O
1d
Trace
5
1e
90
6c)
1f
36
a) Olefin (1.0 mmol), Nucleophile (2.0 mmol), Cu (OTf) 2 (0.05 mmol), Benzene (2 mL), at 70 oC, for 24 h, under Ar.. b)Isolated yield c) Reaction run at 50 oC
㌃⸅ᇦࠍ↪ߚ⚛᳞ᩭߩࠝࡈࠖࡦ߳ߩ
ઃടᔕߩᔕᯏ᭴
㘃ૃߩᔕߢߪ㧘ࠝࡈࠖࡦ㘃߇㊄ዻߦࠃߞߡᵴ ᕈൻߐࠇߡ⚛᳞ᩭߣߩᔕ߇ㅴⴕߔࠆ႐วߣ㧘
㊄ዻ߇⚛᳞ᩭࠍᵴᕈൻߔࠆߎߣߢࠝࡈࠖࡦ 㘃ߣߩᔕ߇ㅴⴕߔࠆ႐วߣ߇ႎ๔ߐࠇߡࠆ 2)㧚 ߒ߆ߒᧄᔕߦ߅ߡᚒޘߪ㧘TfOHߩࠃ߁ߥࡉ
ࡦࠬ࠹࠶࠼㉄ߩߺߢ߽ᔕ߇ૐ₸ߥ߇ࠄㅴⴕߔ ࠆߣ߁ࠃ߁ߥ㧘ᓥ᧪ߩᔕᯏ᭴ߢߪ⺑ߢ߈ߥ
⚿ᨐࠍᓧߚߎߣ߆ࠄ㧘ᧄᔕߢߪ㌃ߣ㉄ߩਔᣇ߇⸅
ᇦߣߒߡߡࠆߣ⠨߃ߚ㧔Scheme 8㧕㧚
߹ߕ㧘ࠤ࠻㧙ࠛࡁ࡞ᄌ⇣ᕈߦࠃࠅࠛࡁ࡞ൻ ߒߚ⚛᳞ᩭߦ㌃߇㈩ߒ㧘⚛᳞ᩭࠍᵴᕈൻ ߔࠆ㧚ߎߩᤨߦTfOH߇⊒↢ߔࠆޕߎࠇ߇ࠝࡈࠖ
ࡦߣᔕߒߡࠞ࠴ࠝࡦਛ㑆ࠍ↢ᚑߒ㧘㌃ߦࠃࠅᵴ ᕈൻߐࠇߚ⚛᳞ᩭߣᔕߔࠆߎߣߢ⋡⊛ߩઃ
ടᔕ߇ㅴⴕߒ㧘㌃߇ౣ↢ߐࠇࠆߣ⠨߃ࠄࠇࠆ㧚 TfOHࠍ⸅ᇦߦ↪ߚᤨߢ߽㧘ࠞ࠴ࠝࡦਛ㑆ߣࠛ
ࡁ࡞ߣ߇ᔕߔࠆߎߣߢ⋡⊛‛߇↢ᚑߔࠆ߇㧘ࠞ
࠴ࠝࡦਛ㑆߇ࠬ࠴ࡦߣᔕߔࠆߎߣߢࠬ࠴
ࡦߩੑ㊂ൻ߇ㅴⴕߔࠆ㧚߅ߘࠄߊ㧘㌃㧙ࠛࡁ࠻
ਛ㑆ߣࠬ࠴ࡦߣࠛࡁ࡞ߩᔕᕈߩ㆑ߦࠃ ࠅᔕߩㆬᛯᕈ߇Ꮐฝߐࠇࠆߩߢࠈ߁ޕ
TfO R1 R2
O O
R
R1 R2 OCuO
OTf
R
Cu OTf OTf
R1 R2
O O
R1 R2 O OH
R1 R2 OCuO
OTf
TfOH R
TfO
R
R
R R
Scheme 8
㧠 ⚿⸒
ㆫ⒖㊄ዻ⸅ᇦࠍ↪ߚࠝࡈࠖࡦ㘃ߣ᳞ᩭߩ
⸅ᇦ⊛ઃടᔕߪ㧘Ყセ⊛ଔߢᚻኈᤃߥ⊒ේ
ᢱߩ⚵ߺวࠊߖ߆ࠄઃടଔ୯ߩ㜞⺃ዉ߇ᓧࠄ ࠇࠆߚ㧘㕖Ᏹߦ↪ߥᔕߢࠆߣ߃ࠆ6)㧚ߘ ߩ᭽ߥᔕߩ߭ߣߟߣߒߡ㧘ߏߊᦨㄭႎ๔ߐࠇߚ 1,3-ࠫࠤ࠻ࡦ㘃ࠍ⚛᳞ᩭߣߔࠆࠝࡈࠖࡦ㘃߳
ߩ⸅ᇦ⊛ઃടᔕߢߪ⸅ᇦߣߒߡ㜞ଔߥ AuCl3߿ ขࠅᛒߦߊ AgOTf ࠍ↪ࠆߥߤታ↪ᕈߦ߆ߌ ࠆ߽ߩߢߞߚ㧚
ᧄ⎇ⓥߢߪଔߢขࠅᛒ߿ߔ㌃⸅ᇦࠍ↪
ߡࠃࠅታ↪⊛ߥᔕࡊࡠࠬߩ㐿⊒ࠍ⋡ᜰߒ㧘Ǫ㧙
ࠫࠤ࠻ࡦ㘃ߥߤߩ⚛᳞ᩭߩࠝࡈࠖࡦ㘃߳ߩ
ઃടᔕߩᬌ⸛ࠍⴕߞߚ㧚
ࠝࡈࠖࡦ㘃ߣߒߡࠬ࠴ࡦ㧘⚛᳞ᩭߣߒߡ
ࠫࡌࡦ࠱ࠗ࡞ࡔ࠲ࡦࠍ↪ߡ㧘ฦ⒳ᔕ᧦ઙࠍᬌ⸛
ߒߚߣߎࠈ㧘㌃⸅ᇦߣߒߡCu(OTf)2㧘⸅ᇦ㊂5 mol%㧘 ࡌࡦࡦṁᇦਛߢ㕖Ᏹߦ㜞⸅ᇦᵴᕈࠍ␜ߔߎߣ ߇ࠊ߆ߞߚ㧚એߩ⚿ᨐࠍ〯߹߃ߡ㧘⚛᳞ᩭߦ ࡌࡦ࠱ࠗ࡞ࠕ࠻ࡦ㧘2,4-ࡍࡦ࠲ࡦࠫࠝࡦ㧘3,5-ࡋࡊ
࠲ࡦࠫࠝࡦ㧘2-ࠕ࠴࡞ࠪࠢࡠࡍࡦ࠲ࡁࡦߣ㧘ࠝ
ࡈࠖࡦߣߒߡࠬ࠴ࡦߣߩᔕࠍⴕߞߚ⚿ᨐ㧘㜞
₸ߢ⋡⊛ߩઃട߇ᓧࠄࠇߚ㧚ࠕ࠻㈶㉄ࡔ࠴࡞ࠍ
↪ߚ႐วߢ߽₸23%ߢઃട߇ᓧࠄࠇߚ㧚߹ߚ㧘
ࠬ࠴ࡦ㘃એᄖߦ߽2-ࡁ࡞ࡏ࡞ࡀࡦ߿1,3-ࠪࠢࡠࡋ
ࠠࠨࠫࠛࡦߥߤ߽ࠝࡈࠖࡦၮ⾰ߣߒߡᵴᕈࠍ␜
ߔߎߣ߇ࠊ߆ߞߚ㧚
એㅀߴߚࠃ߁ߦ㧘㌃⸅ᇦࠍ↪ࠆߎߣߦࠃߞߡ
⚛᳞ᩭߩࠝࡈࠖࡦ㘃߳ߩઃടᔕߦ߅ߡ㧘 ߎࠇ߹ߢႎ๔ߐࠇߡߚၮ⾰ߦട߃㧘ߐࠄߦᓎࠫ
ࠛࡦ㘃㧘ࠤ࠻ࠛࠬ࠹࡞㘃ߥߤ㧘ၮ⾰ㆡ↪▸࿐ߩᄢ ࠍ㆐ᚑߒ㧘⚛㧙⚛⚿วᒻᚑᔕ߇ࠃࠅ৻⥸⊛ߦ ㅴⴕߔࠆߎߣࠍࠄ߆ߦߒߚ㧚
ᦨᓟߦ㧘ห⎇ⓥ⠪ߩદ⮮ཅᒾቴຬᢎ߇ᤓᐕ 1223ᣣߦᔃਇోߢㅤߐࠇߚޕవ↢ߩߏࠍ
ࠅ߹ߔޕ
ෳ⠨ᢥ₂
1) M. Meller, J. Seayad, A. Tillack and H. Jiao, “Catalytic Markovnikov and anti-Markovnikov functionalization of alkenes and alkynes. Recent developments and trends,”
Angew. Chem. Int. Ed., 43, 3368–3398 (2004).
2) (a) X. Q. Yao and C.-J. Li, “Highly Efficient Addition of Activated Methylene Compounds to Alkenes Catalyzed by Gold and Silver,” J. Am. Chem. Soc., 126, 6884–6885 (2004).
(b) X. Q. Yao and C.-J. Li, “Highly Efficient, Reversible Addition of Activated Methylene Compounds to Styrene Derivatives Catalyzed by Silver Catalysts,” J. Org. Chem., 70, 5752–5755 (2005).
3) ᳰ ྾㇢, ታ㛎ߩߚߩṁᇦࡂࡦ࠼ࡉ࠶ࠢ, ਣༀ
(1990).
4) Y. Ito, R. Kato, K. Hamashima, Y. Kataoka, Y. Oe, T. Ohta and I. Furukawa, “Intramolecular Cyclization of Phenol Derivatives with C=C Double Bond in a Side Chain,” J.
Organomet. Chem., 692, 691–697 (2007).
5) D. C. Rosenfeld, S. Shekhar, A. Takemiya, M. Utsunomiya and J. F. Hartwig, “Hydroamination and Hydroalkoxylation Catalyzed by Triflic Acid. Parallels to Reactions Initiated with Metal Triflates,” Org. Lett., 8, 4179–4182 (2006).
6) (a) Y. Oe, T. Ohta and Y. Ito, “Ruthenium catalyzed addition reaction of carboxylic acid across olefins,” Chem.
Commun., 1620–1621 (2004). (b) Y. Oe, T. Ohta and Y. Ito,
“Ruthenium-Catalyzed Addition Reaction of Alcohols across Olefins,” Synlett, 179–181 (2005). (c) T. Ohta, Y.
Kataoka, A. Miyoshi, Y. Oe, I. Furukawa and Y. Ito,
“Ruthenium-Catalyzed Intramolecular Cyclization of Hetero-functionalized Allylbenzenes,” J Organomet. Chem., 692, 671–677 (2007).
