An Improved Suzuki-Miyaura Cross-coupling Reaction for Synthesis Fluorine Substituted 3-Biaryl-1-ferrocenyl-2-propen-1-one - PowerPoint PPT Presentation

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An Improved Suzuki-Miyaura Cross-coupling Reaction for Synthesis Fluorine Substituted 3-Biaryl-1-ferrocenyl-2-propen-1-one

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Title: An Improved Suzuki-Miyaura Cross-coupling Reaction for Synthesis Fluorine Substituted 3-Biaryl-1-ferrocenyl-2-propen-1-one


1
?????? ????????
???
2
?????
1959???,????? 1983.7,
???????????,???? 1997.6,
??????????????,??????? 19831998,
????????????????,????
?,?????????? 19972001, ?????????????? ???
???????? ??? 2002,
????????????????  ????????,?????????
3
???? Ar-Ar ????
1.???(Ullmann,1901?)??
2.????(2005?CA????320??)
  • A. Suzuki-Miyaura Cross-coupling Reaction
  • RX RB(OH)2 R-R

B. Heck Cross-coupling Reaction RX
R-CHCH2 R-CHCH-R
C. Stille Cross-coupling Reaction RX
R-SnR3 R -R
4
D. Sonogashira
E. Negishi Cross-coupling Reaction RX
R-ZnX R -R
??????
????Hiyama ?????? N, O??(?\???????)
5
??? Suzuki-Miyaura ??????
6
?. ?????????
??Ullmann????????????,???????????????????????
?????? ??Ullmann???????????(??200?),?????????.
????????????,??????????????????????????????????
????????????????????,???????????????????


?1-1
7
1972?,Tamao, K.?Kumada, M. ?? Corriu, R. J. P.
?????????????????????Ni(II)???????????????????
?1-2
J. Am. Chem. Soc. 1972, 94, 4374-4376. J. Chem.
Soc. Chem. Commun. 1972, 144-144.
8
Sekiya, A.? Ishikawa, N.?1976?,????????? ?
????? ?
J. Organomet. Chem. 1976, 118, 349-354.
9
Kende, A. S. ???1975?????????????????????,
Negishi, E.-I. ????????????????????,??????????????
??????????????????,???????????????????????????????
???????????,? Murahashi, S.??????,Migita,
T.?Stille, J. K.??????,Normant, J. F.
???1-??,Hiyama, T. ????????????
10
Miyaura, N.?Suzuki, A.?1981?????????? ??????????
Synth. Commun. 1981, 513-519
11
X Cl, Br, I R, R ??, ??, ?? ????Pd(0)?,
??Pd(OAc)2, Pd(PPh3)2Cl2, Ni(0),
Ni(PPh3)2Cl2 ?---- ???
12
  • Suzuki?????????????????????????????
    ???,?Suzuki???????????????????????,??????????????
    ?,??????????,?????????????????????????????????????
    ????????????,Suzuki?????????????
  • ?????????, ??????, ????, ??????
  • ?????????
  • ??????????????????,?????????????,?????????????

13
?. Suzuki-Miyaura ???????
1.???(?)????
2.????????
3.???????????????
4.??????????
???
Smith, G. B. J. Org. Chem. 1994, 59, 8151-8156.
14
1992?,Snieckus V.????????????????????
Tetrahedron Lett. 1992, 33, 2253-2256. J. Org.
Chem. 1998, 63, 7536-7538. Eur. J. Org. Chem.
1998, 4, 701-709.
15
1995?,Tschierske C.?????????????? ??????????
J. Chem. Soc., Chem. Commun. 1995,645-646.
16
1997?,Abell C.????????????,??Suzuki-Miyaura???????
???????,?????????,??????????????????????
? 1-16
Tetrahedron Lett. 1997, 38, 6781-6784.
17
1992?,McKillop A. ???????????????????????????
?,????Pd(PPh3)4???????????????????????????????????
??,?????????????????????????????????,?????????,???
??
Ali, N. M. McKillop, A. Mitchell, M. B.
Rebelo, R. A. Wallbank,P. J. Tetrahedron 1992,
48, 8117-8126
18
1997?,Wong H. N. C.?Ye X.-S.???Suzuki ????????????
??,?????
J. Org. Chem. 1997, 62, 1940-1954.
19
?. ??
??????,Suzuki???????????????????,???????,?
????Suzuki??????????,????????????
20
1. ?????????
????Suzuki-Miyaura????????????Pd(PPh3)4
?????,?????????????????????????,??????????????????
?????????????????????????????(?1-10mol),?????????
??????????,????????????????????,
????????????????????
21
2. ?????????
????Suzuki???????????????????,????????????????
?,???????????????????????????????????????????????,
???????????????,??????????????,?????,??,??,????,??
??Suzuki-Miyaura??????,???????
22
??????????????????????????????,???????????????
?????????????????????????????,???????????????,????
?????????????????????1998???,?????????????????????
???????????Fu G. C. ?Herrmann W. A., ???Buchwald
S. L.?????????????????????????,???????????????(??
??)??,????,??-????,????????????????
23
3. ?????Suzuki-Miyaura??????
???????????????????????????????????,??????
?????????????,???????????,????????????????????????
????,??????????????????????, ???????,???????,?????
??? ??????????Suzuki?????Larhed
M.?Hallberg A.61??,??Pd(PPh3)4??,?????????????????
????,???,???DME???????
24
Schotten T.??????????????????????,???????
???????????,??????,???????2?????2-4?????????,?????
???????????,??,?????????????????????????????
25
??,Villemin D.????????????????? ?????????????????
????
Tetrahedron Lett., 1996, 37, 8219-8222. J. Org.
Chem. 1999, 64(11), 3885-3890. Tetrahedra Lett.
2001, 42, 635-637.
26
4. ?????Suzuki-Miyaura??????
Badone D.?????????????????,?????????TBAB??????
??????????????Suzuki????,???????ArB(OH)3-Bu4N,??
???????(?1-27)65?
?????????????????,?????????????,?????????Ar
B(OH)3-R4N,???????????
27
Leadbeater N. E. ??????????????????????,??
????????????????????TBAB?Pd(OAc)2??????????1110
.0043.8, ????????????,????100W????,??????
?1.3?????????? 5min,??????????????????4-???????,??
??99.
J. Org. Che m. 2003, 68, 888-892.
Li, C. J Angew. Chem. Int. Ed. 2003 , 42,
4856-4858
28
Bumagine N. A.???????????????????????????????S
uzuki??????????????(Na2CO3, NaOH)????????????,????
?????????????,??????????????????,??????.
?1-27
Tetrahedron 1997, 53, 14437-14450.
29
  • ????Suzuki-Miyaura??????????
  • ?????????????????, ??????,
  • ???????, ?????. ?????GDP??????
  • ????.

Blettner C. G. ?????????????PEG???Suzuki??
????????????PEG6000 (?????0.33m
equiv/g),??????(???2-???)?1.2??????,????75W??????1
2??,?????????95????????,?????PEG?????900W???10mi
n?????????????????????73,?????PEG???????8?
????????????????????PEG,???????????PEG?????????
?,???4-??????????????????PEG,?70W?????4min,???????
91,?????86?
J. Org. Chem. 1999, 64(11), 3885-3890.
30
??? Suzuki-Miyaura ???????
31
????
????RI gtRBr gtRCl
??????
Miyaura, N. Suzuki, A.. Chem. Rev. 1995, 95,
2457-2483
32
??,Suzuki, A.???????????????????????????,????
???????????????????????
J. Organomet. Chem. 1999, 576, 147-168
33
??? ???????? ?????????????
34
?. ?????????????????
??1987?,Green M. L. H.????????????????(SHG
)???????,?????????????NLO????????????,????????????
??????????????????,???????????(NOL),????,???,????,
???????????????????? ????????????????????
?????,???????????????Green?????,??????????????????
???,?????????????????????????????,????????????????
?????????????????,?????????????????,?????????????
,????????????????????????????????????????????????
?
35
????????????????????p?????????????,??????
??????,???????????????????????????????????????????
?????????????????????? ??????????????????,
????????????18????,?????????,????????????d????,d??
?????????????,???????????,???????????????????????,
?????????????(??,??,???,?????????)???,????????????
?????????????,????????????????? ????
??????,??????????,???????? ??????????????????
?????????????????????????
36
Synthesis and Structure of (cis)-1-Ferrocenyl-2-(
4-nitrophenyl) Ethylene, An Organotransition
Metal Compound with a Large Second-order Optical
Nonlinearity. Green, M. L. H. Marder, Seth
R.Nature 1987, 330, 360-362.
37
Review Organometallic Compounds for Nonlinear
Optical-The Search for En-Light-enment. N. J.
Long Angew. Chem. Int. Ed. Engl. 1995, 34,
21-38.
38
(No Transcript)
39
Studies of the Electronic Structure of
Metallocene-Based Second-Order Nonlinear Optical
Dyes Marder, S. R. J. Am. Chem. Soc. 1999
121(15) 3715-3723.
40
Preparation of (Thiophene)manganese Tricarbonyl
Cations for Nonlinear Optics Lee, I.
S. Seo, H. Chung, Y. K.Organometallics 1999
18(6) 1091-1096.
41
(No Transcript)
42
Third-Order Nonlinear Optical Properties of
Donor-Acceptor Organometallic Compounds in Films
and Solution Rojo, G. Agullo-Lopez, F. Campo,
J. A. Heras, J. V. Cano, M.J. Phys. Chem. B.
1999 103(50) 11016-11020.  
43
Systematic Study of the Structure-Property
Relationship of a Series of Ferrocenyl Nonlinear
Optical Chromophores, Robinson, B. H. J.
Am. Chem. Soc. 2005 127(8) 2758-2766.
44
  • ?????????????????
  • ????,??????

????????
45
????????
????????? ??????????????? ?? Ar-Ar
????? ??????--??
46
??????????
Synth. Commun., 33, 3935-3941, 2003 Chin. Chem.
Lett., 14(6), 569, 2003
47
(No Transcript)
48
Molecules, 2005, 10, 670
Synth. Commun., 34(12), 2223, 2004
Chin. Chem. Lett., 16(1), 132, 2005
49
  • ????????
  • ??????,??24????,???72????
  • ?????
  • ????(?????????)?

50
????????????,??????
51
Table 1. The Suzuki cross-coupling reaction of
1-ferrocenyl-3-(4-bromophenyl)- 2-propen-1 -one
with 3,4,5-trifluorophenylboronic acid with Pd(0)
catalyst.a
Table 1. ???????
52
(No Transcript)
53
a 20mg 1-ferrocenyl-3-(4-bromophenyl)-2-propen-1-
one, 11.6 mg 3,4,5-trifluoro- phenyl boronic
acid, 0.2 mL sodium carbonate aqueous
solution (2 M), 15 mL solvent, 3 mmol
Pd(PPh3)4. All materials were added with step by
step under N2 atmosphere in entry
126.(??????????) ball solvents were untreated
before using. c 5 (n-C4H9)4NCl- (70 in water)
were added as phase transfer catalyst. d All
materials were mixed at the same time under N2
atmosphere. (????????)
54
Table 2. ??????????????????a
???????
55
Table3. ????????????
Synthesis, 2006,No.1,123-127.
56
????
57
  • ?????????
  • ??????????

58
Figure 1. UV-visible absorption spectra of 3c in
Various Solvents. (hexane, Et2O, THF, CH2Cl2 ,
acetone, DMF, EtOH)
59
hexane, Et2O, THF, CH2Cl2 , acetone, DMF,
EtOH
60
Table 1. UV Spectra data of 3a-3g in Various
Solvents.
hexane Et2O THF CH2Cl2 DMF EtOH
3a 300nm 480nm 308nm 494nm 314nm 502nm 308nm 508nm 324nm 512nm 322nm 514nm
3b 318nm 480nm 322nm 494nm 326nm 496nm 326nm 510nm 330nm 502nm 332nm 514nm
3c 330nm 484nm 334nm 498nm 338nm 492nm 342nm 510nm 342nm 514nm 342nm 516nm
3d 316nm 478nm 318nm 492nm 324nm 494nm 326nm 512nm 324nm 504nm 332nm 514nm
3e 298nm 488nm 302nm 496nm 306nm 500nm 300nm 512nm 318nm 510nm 320nm 516nm
3f 298nm 490nm 298nm 496nm 306nm 502nm 310nm 516nm 322nm 514nm 324nm 522nm
3g 298nm 486nm 298nm 494nm 312nm 498nm 308nm 508nm 320nm 512nm 322nm 518nm
61
?????? ????????????????????????????,
??????????(????????)?480nm ??????2836nm
,?300nm??????12nm26nm. ??????
1. ???????, ?????p???(??)??? 2.
???????, ????????????????????.(SHG)
62
??????????
63
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