Pd () :

1. Suzuki 2. Heck 3. Sonogashira

Pd :

Suzuki

1. SuzukiSuzuki-Miyaura 1.1 Suzuki

1. Suzuki Pd(0)-Pd(II) Pd(II)-Pd(0) 1.2 Suzuki

1. 1.3 Suzuki1.2.3.Suzuki 1. 2. Suzuki3. Suzuki

2. (), ()()2.1

2. Grinard

2. , 1995Ishiyama: (yield: 60-98%), -2.2

2. 1. DMSO DMF > dioxane > toluene 2. KOAcK3PO4K2CO33. Pd(dppf)Cl24. 2001Ishiyama Pd(dba)2/2.4PCy3(3-6mol %)

2.

2. 2.3 2.4

3. Suzuki1. Suzuki-couplingPd(0)-Pd(II) I > TfO > Br >> Cl2. -Pd(II)-arylaryl > alkylaryl > n-propyln-propyl > ethylethyl > methylmethyl3. SuzukiPd(PPh3)4PdCl2PdCl2(dppf)Pd(OAc)2Pd(PPh3)2Cl2NiCl2(dppf)

3. SuzukiSuzuki K2CO3K3PO4Na2CO3CsFCs2CO3t-BuONa,NaHCO3toluene/EtOH/H2O, CH3CN /H2Odioxane/H2O3.1 Suzuki

3. Suzuki SuzukiSuzuki, , NaOHBa(OH)2, DME2,4,6-: Ba(OH)2> NaOH > K3PO4 > Na2CO3 > NaHCO3, 3.2 Suzuki

3. Suzuki

3. Suzuki2-2-Na2CO3DME80, 39%. : , K3PO4, DMF, 89%Suzuki 3.3 Suzuki

3. SuzukiSuzuki Suzuki

3. SuzukiSuzuki 3-,3.4 Suzuki

3. Suzuki()Suzuki, TlOHTl2CO3, Suzuki, , , Suzuki3.5 Suzuki

3. Suzuki3.6 Suzuki

3. Suzuki3.7 TriflateSuzuki , PPh3Triflate, LiBrKBr

3. SuzukiMitchelldppbSuzuki98%; Wang Shen(PCy3)Pd(PCy3)Cl2 3.8 Suzuki

3. SuzukiSyun Satio,80NiCl2(dppf) (10 mol%)n-BuLi(40 mol%). NiCl2(PPh3)280% 3.9 Suzuki

3. Suzuki3.10 PdCl2Pd(OAc)2Pd/CHiroaPd/C Suzuki

3. SuzukiD. S. EnnisPd /C Suzuki-couplingSB-245570Pd(OAc)2Suzuki

Heck

1. Heck Heck2060Heck Morizoki,,C-CHeckTrans

2. Heck Heck

1Oxidative addition: RX (RX=I > TfO > Br >> Cl)Pd0L2Pd

2 Cordination-insertion:Pd-R 3-H

4Pd0L2

3. Heck Heck 1972Mori Ban1977HeckHeck

4. Heck DanishefskyTaxol4.1

4. Heck 2080Heck1989Shibasaki Overman HeckOvermanHeck 4.2

physostigmineHeck4.Heck

4. Heck Zeigler HeckHeckOverman Heck4.3

5. Heck Heck SP3SP3

5.1 Heck

5. HeckPd-HCurtin-HammettR CN,Wittig-Horner

5. Heck 1992Tamio HayashiHeck5.2Heck

, 18-N,N-1a96%ee 26-1a69%ee5.Heck

5. Heck5.3 Heck 5.3.1 BellerHeck

5. Heck

5.3.2 HeckHeck

5. Heck

5.3.3 Heck0.005 mol%

5. Heck

5.3.4 Heck20

Sonogashira

1. Sonogashira Sonogashira,

2. SonogashiraSonogashira(II)(CuI)

2. SonogashiraSonogashiraSonogashira

3. Sonogashira 1. 2. 3. 4.

Sonogashira

3.1 Pd(OAC)2PPh3CuINHCDMF

LiSonogashiraDABCO,Sonogashira,0.0001 mol%7200003.1

3.2 Elangovan2Sonogashira 3.2.1 (CuI)

Pd(OAc)2, Pd2(dba)3, PdCl2(dppf), PdCl2(PPh3)2, PdCl2(PCy)2, PdCl2, PdCl2(CH3CN)2Cs2CO3, Bu4NOAc, TBAF, Pyrrolidine, TEA, DBACO 3.2 3.2.2

3.3

3.3

3.3 3.3.1

3.3.2 3.3

3.3.3 3.3

3.3.4 3.3

3.4 SonogashiraHopkinsSonogashira Sonogashira

McLaughlinSonogashira3.4 LuSonogashiraCacchi

3.4 ,-

, 3.4

Question & Comments