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Chiral gold-catalyzed asymmetric reactions. 报告人:刘槟. 2012 年 5 月 26 日. Diphosphine ligands controled Chiral gold(I) Catalysts. 1. 2. 3. (1). (2). 4. 5. Antonio M. Echavarren . Angew . Chem. Int. Ed . 2004 , 43, 2402 –2406. 6. (1). (2). (3). 7. 8. 9. 10. - PowerPoint PPT Presentation
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Chiral gold-catalyzed asymmetric reactions
报告人:刘槟 2012年 5月 26日
Chiral gold Catalyst
Chiral gold(I)
Diphosphine ligand
monophosphine ligand
Chiral Carbene
Chiral Anion
Chiral gold(III)
Type of Chiral gold Catalyst
Ross A. Widenhoefer. Chem.Eur.J. 2008,14, 5382-5391Xiaodong Shi. ChemCatChem. 2010, 2, 609-619Veronique Michelet. Synthesis. 2011, 10, 1501-1514
From 1986 to now, more than fifty papers including three reviews:
Some leading groups : F. Dean Toste Ross A. Widenhoefer Veronique Michelet etc.
Diphosphine ligands controled Chiral gold(I) Catalysts
Fe
RCHO +CN
[Au(CyNC)2]+BF4- (1 mol%)
L* (1 mol%)
DCM , 25oCO N
R COX
O N
R COX
+
trans cis
R = Ph, 98%, 89:11R = (E)-MeCH=CMe, 89%, 91:9R = t-Bu, 100%, 100:0
96% ee95% ee97% ee
49% ee31% ee
--
NMe
H
PPh2
PPh2
NO
Au+
O
R
NO-
OMe
L*
XO
NMe
OMeX =
X = OMe,X = OMe,X = OMe,
Yoshihiko Ito, Tamio Hayashi. J. Am. Chem. Soc. 1986, 108, 6405-6406
R = Ph , 97:3R = i-Pr, 98:2R =(E)-MeCH=CHCHO, 97:3,
86% yield , 96% ee90% yield , 97% ee94% yield , 99% ee
Yoshihiko Ito. J. Org. Chem. 1995,60, 1727-1732
1.
EtOOC
EtOOC RL*(AuCl)2
H2 (4 bar), EtOH20-45 oC
EtOOC
EtOOC R
Ph
MeN
R = HR = PhR = 2-Naphthyl
20% ee80% ee95% ee
Ph
or
Ph
MeNH
Ph
or
75% ee
P
PL*=
L* AuClH2
L* AuH
AuL*
H R1 R2
Au*L
R1R2
Au OEt*L
R1 R2
R2R1
H2
EtOH
Proposed Mechanism
Avelino Corma,Chem. Commun., 2005, 3451-3453
2.
MeOOC COOMe
R
L*(AuCl)2 (5 mol %) , AgOTf (15 mol %)
MeNO2 , r.t.
MeOOC COOMe
R
MeOOC COOMe
R
+
3.572% ee
1
PAr2
PAr2Ar =L* =
R = Me , R' = H
R = Ph , R' = H
R = R' = Me
1.545% ee
1
R' R' R'
559% ee
1
Michel R. Gagne. Angew. Chem. Int. Ed. 2007, 46, 6670-6673
3.
(1)
(2)
NHTs L*(AuCl)2 (3 mol %)AgX (6 mol %)
DCE , 23oC
TsN
X = BF4X = OBzX = OPNB
82% , 1% ee27% , 98% ee76% , 98% ee
F. Dean Toste. J. Am. Chem. Soc. 2007, 129, 2452-2453
PAr2
PAr2Ar =L* =
NHCbz
PhPh
L*(AuCl)2 (2.5 mol %)AgClO4 (5 mol %)
m-xylene , -40oC97% , 81% ee
CbzN
PhPh
MeOMeO
PAr2
PAr2Ar =
t-Bu
t-Bu
OMeL* =
Ross A. Widenhoefer. Org Lett. 2007, 9, 2887-2889
X
NHCbz
R2
R1
L*(AuCl)2 (2.5 mol%)AgClO4 (5 mol%)
m-xylene23oC , 24h
X
CbzN R1
R2 X
CbzN R1
R2
+
(Z) (E)
X = CPh2 , R1 = Me , R2 = EtX = CPh2 , R1 = Me , R2 = n-hexylX = CPh2 , R1 = Me , R2 = t-Bu
94% (3.1:1) 96%ee / 76%ee99% (10.1:1) 91%ee / 9%ee52% (<=1:2.5) 2%ee / --
X
NHCbz
Et
Me
X
NHCbz
Et
Me
L*(AuCl)2 / AgClO4
L*(AuCl)2 / AgClO4
X
NHCbz
Et
MeAuL
L*(AuCl)2 / AgClO4
X
NHCbz
Me
EtAuL
X
N
EtMe
H AuCbzH
X
N
MeEt
H AuCbzH
X
CbzN
EtMe
H
(R,Z)
X
CbzN
MeEt
H
(R,E)
Ross A. Widenhoefer. J. Am. Chem. Soc. 2007, 129, 14148-14149
NH
COOEtCOOEt
OHNH
COOEtCOOEt
L*(AuCl)2 / AgOTf =1:2
toluene95% , 90%ee
MeOMeO
PAr2
PAr2Ar =
t-Bu
t-Bu
OMeL* =Marco Bandini. Angew. Chem. Int. Ed. 2009, 48, 9533-9537
4.
NHR
PhPh OH
L*(AuCl)2 (2.5 mol%)AgClO4 (5 mol%)
dioxane , 25oC
RN
PhPh
H
NHR
PhPh OH
[L*Au2]2+ NHR
PhPh OH
[L*Au2]2+
N OHH
PhPh
R
H[L*Au2]2+
N OH2PhPh
R
H[L*Au2]2+
RN
PhPh
H
-H2O-[L*Au2]2+
R = Fmoc , 95% ,91%ee
Ross A. Widenhoefer. Angew. Chem. Int. Ed. 2012, 51, 1405-1407
O
Ph
R
L*(AuCl)2 / AgOTf =1:2
toluene OR
PhH
R = 4-MeOC6H4R = Et
56% , 96%ee24% , 91%ee
TsNPh
L*(AuCl)2 / AgOTf =1:2
toluene TsNPh
H
r.t.40oC60oC
11% , 78%ee47% , 98%ee74% , 98%ee
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
Veronique Michelet.Chem. Commun., 2009, 6988-6990
XR
[M] = Pt, Au, Ir
XR
H
[M]
XR
H
[M]-H
XR
H
-[M] H
XR
Proposed intermediates
5.
Antonio M. Echavarren. Angew. Chem. Int. Ed. 2004, 43, 2402 –2406
PhO2S
PhO2S
R L*(AuCl)2 (1.6 mol%)AgSbF6 (2 mol%)
MeOH , r.t.
PhO2S
PhO2S
R
OMe
R = HR = Ph
89% , 53%ee52% , 94%ee
L* = PTol2PTol2
Antonio M. Echavarren. Organometallics.2005, 24, 1293-1300
ROOC
ROOC
Ph
+NMe
L*(AuCl)2 (3 mol%)AgOTf (6 mol%)
Et2O , r.t.
ROOC
ROOCN Me
H HPh
R = MeR = i-Pr
99% , 83%ee94% , 99%ee
MeOOC
MeOOC
L*(AuCl)2 (3 mol%)AgOTf (6 mol%)
Et2O , r.t.
MeOOCMeOOC
99% , 93%
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
Veronique Michelet. Chem. Eur. J. 2009, 15, 1319-1323
6.OPiv
+ Ar
(R)-DTBM-SEGPHOS(AuCl)2 (2.5 mol%)AgSbF6 (5 mol%)
MeNO2 , r.t.Ar
PivO76-94% ee
Ph
H OAc+ Ph
PPh3AuCl (2 mol%)AgSbF6 (2 mol%)
65%
PhPhPivO
91% ee >95:5 cis:trans, 95:5 Z:E, 0%ee
Ph
OAc L-Au
AuOAc
Ph
L
Ph
Ph
PhOAc
Ph
PhOAc
Ph
Mechanistic Hypothesis
F. Dean Toste. J. Am. Chem. Soc. 2005, 127, 18002-18003
(1)
Me OAc(R)-xylyl-BINAP(AuCl)2 (2.5 mol%)
AgSbF6 (5 mol%)
MeNO2 , -25oC
Me OAc
92% ee
F. Dean Toste. J. Am. Chem. Soc. 2009, 131, 2056-2057
(2)
(3)O
Me OPiv
Ph
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
L*(AuCl)2 (5 mol%)AgSbF6 (10 mol%)
MeCN, r.t.O
OPiv
Ph
74% , 97% ee
O
Me OPiv
Ph
LAu+
O
Ph
AuL
OPiv
O
Ph
OPiv
AuL
O
OPiv
Ph
O
OPiv
AuL
Ph
T.M.
Proposed Mechanisms
F. Dean Toste. J. Am. Chem. Soc. 2009, 131, 3464-3465
NO
Ph
Me
O
L*(AuCl)2 (5 mol%)AgY (5 mol%)
MeCN , 25oCN
O
O
Me
Ph
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
NO
Ph
Me
O
H
NO
H
O
Me
Ph
AuLFirstCyclization
1,5-H shift
NO
OMe
Ph
AuL
H
Junliang Zhang. Chem. Eur. J. 2011, 17, 3101-3104
7.
N NHt-Bu
O
+ Me5
L*(AuCl)2 (2.5 mol%)AgOTf (5 mol%)
m-xylene , 100oC
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
N Nt-Bu
O Me
Me5
Ross A. Widenhoefer. J. Am. Chem. Soc. 2009, 131, 5372-5373
86% , 76% ee
Markovnikov product
OHPh
L*(AuCl)2 (2.5 mol%)MX (5 mol%)
DCE , -30oC
O
Ph
MX = AgNTf2MX = NaBRAF
86% ee91% ee
Na+
B-
FF
F
FFF
F FF
FFF
FF
F
FFF
FFF
F FF
NaBARF
MeOMeO
PAr2PAr2
Ar =
t-Bu
t-Bu
OMeL* =
Proposed Mechanism
OHPh
OPh
[AuL]+
X-
H
[LAu]+ X-O
Ph[AuL]+ X-
H+
O
Ph
F. Dean Toste. J. Am. Chem. Soc. 2009, 131, 9178-9179
8.
ON
O
R2
R1
ON
O
R2
R1 Au
ON
OAu
R2
R1
R3 NR1 COOHR2
R3
ON
O
R1
R3R2
NHSO2R
(S)-Cy-SEGPHOS(AuOBz)2
(R)-xylyl-SDP(AuOBz)2
RO2SN R3
F. Dean Toste. J. Am. Chem. Soc. 2011, 133, 3517-3527
PAr2
PAr2
Ar = 3,5-xylyl
xylyl-SDP
9.
R
L*(AuCl)2 (5 mol%)AgSbF6 (20 mol%)
1:9 DCM:DCE , -35oCR
R = Ph
R =
89% , 87%ee
94% , 93%ee
PAr2
PAr2
Ar = 3,5-xylylL*=
Dean J. Tantillo , Michel R. Gagne. Nature Chemistry. 2012, 4, 405-409
10.
Monophosphine ligands controled Chiral gold(I) Catalysts
TsN
[Au] AgSbF6
TsN
H
H
DCM
(R)-DTBM-SEGPHOS(AuCl)2 r.t.(S,S,S)-L1AuCl -15oC(R,R,R)-L2AuCl -15oC
+TsN
H
H
-- (1:1.7) 8%ee82% (14:1) 80%ee82% (16:1) 90%ee
OO P N
Ph
PhL1 = O
O P NPh
PhL2=
TsNR
R
[Au]TsN
R
R+[Au]
TsN[Au]
RRH
H
[4+3]
[4+2]
[2+2]
Jose L. Mascarenas. J. Am. Chem. Soc. 2009, 131, 13020-13030
1.
MeOOCMeOOC
R
R
OO
L1*AuCl (5 mol%)AgBF4 (5 mol%)
up to 92% eeMeOOCMeOOC
RRH
H
TsN
R
RL2*AuCl (5 mol%)AgBF4 (5 mol%)
up to 92% ee TsN
RR
H
H
O
3P
L1*
OO
PNPh
Ph
R'
R'
R' =
L2*
F. Dean Toste. Org Lett, 2010, 12, 200-203
MeOOC COOMe
Ph
L*AuCl (5.5 mol%)AgBF4 (5 mol%)
DCM , 0oC
MeOOC COOMe
H H
PhO
O
O
OP
Ar Ar
Ar Ar
N
Ph
Ph
L* =
91% , >99%ee Ar = 4-(tert-Butyl)phenyl
Veronique Michelet . Angew. Chem. Int. Ed. 2010, 49, 1949 ¨C1953
2.
Similar work by F. Dean Toste using Phosphoramidite Gold(I)
F. Dean Toste . J. Am. Chem. Soc. 2011, 133, 5500–5507
R1
N
H
R2
+ R3 + p-TsNCOL*AuCl (5 mol%)AgNTf2 (5 mol%)
CHCl3 , r.t.
N OR2
R1 R3
NTs
+ N OR2
NTs
R3R1
majormoderate to high regio andenantioselectivities
PPh3
NH
NHOS OO
i-Pri-Pr
i-Pr
L* =
Ph
ArHN O
NHTs
PhLAu
ArHN O
NH Ts
AuLPhPh
ThermodynamicArHN O
NTsH
Ph PhLAu
Kinetic
-AuL+
ArHN O
NTs
PhPh
-AuL+
ArHN O
NTs
Ph Ph
-Favored with small ligands-Increasing rate of protodeauration should futher favor trapping of the kinetic product
Appreciable formation with large ligands
F. Dean Toste .Chem. Sci., 2011, 2, 1369-1378
3.
Chiral Carbene controled gold(I) Catalysts
TsN
Ph
NHC-Au(I) cat.1 (5 mol%)AgSbF6 (5 mol%)
AcOH (20 eq. dry) , DCE0oC
TsN
OAc
HH Ph
>99% , -59% ee
X
Ar
NHC-Au(I) cat.2 (5 mol%)AgSbF6 (5 mol%)
Ph2SO (1.5 eq.) , PhCl4A MS , 10oC
X
86-99% yield, 3-70% ee
CHO
H
Ar N
NHAc
N
AuI
N
N
N
AuIcat.1
cat.2
TsN
Ph
AuL*
TsN
Ph
*LAu
TsN
*LAu
H
Ph
TsN
*LAu
H
Ph
TsN
Ph
HAuL*
H
TsN
Ph
O=SR2TsN
H
Ph
*LAuO
SR2-SR2
TsN
H
Ph
O
TsN
*LAu
H
Ph
NuH
OAcTsN
OAc
*LAu
HPhH
H+
TsN
OAcH
PhH
intramolecular rearrangements of 1,6-enyneShi Min .Organometallics .2011, 30, 3859-3869
NCR
Au(THT)Cl NCR
AuClHNR'2
NR
NR'
R'H
AuCl
R' = i-Pr , R = H (a) R = Ph (b) R = 3,5-(CF3)2C6H3 (c)R' = (S)-MePhCH , R = 3,5-(CF3)2C6H3 (d)
O
Ph
+ i-PrOH(2 eq.)
catalyst (5 mol%)LiNTf2 (4.5 mol%)
DCE
O
Ph
Oi-Pr
cat. = (a)cat. = (b)cat. = (c)cat. = (d)
12% , 8%ee28% , 61%ee68% , 84%ee70% , >99%ee
LeGrande M. Slaughter. Angew. Chem. Int. Ed. 2012, 51, 2912-2915
Chiral Anions controled gold(I) Catalysts
OH
L* = Chiral Diphosphine ligands
L*(AuCl)2 / AgX = 1:1
DCM
OH
52~89% , <10%ee
OH L(AuCl)2 or LAuCl , AgX
Solvent
OH
OO
POO-X =
L = PPh3 (5 mol%) , X (5 mol%) , in DCM
L = dppm (2.5 mol%) , X (5 mol%) , in benzene
R
RR = 2,4,6-i-Pr3-C6H2
89% , 48% ee
90% , 97% ee
A
B
CO
OH(S)-BINAP(AuCl)2 (2.5 mol%)
(R)-AgX(5 mol%)
benzene , 23oC
OH
O
88% , 82% ee
F. Dean Toste. Science, 2007, 317, 496-499
Other Chiral Au(I)/Au(III) Catalysts
NO
N N
O
OHHAu
ClCl
Avelino Corma. Journal of Catalysis, 2009, 265,238-244
N N
Ph Ph
R1R1
R2
R2 R2
R1R1
R2
AuCl
Kiyoshi Tomioka. Tetrahedron Letters. 2010,51,404-406
H
H
AuCl
Constantin Czekelius. Chem. Eur. J. 2009, 15, 13323-13326
PN
ClAu
R'
R'
R
R
P
R
R
P
R
R
NR'
ClAu
ClAu
P
R
R
PR
R
P
R
R
N
AuCl
ClAu
AuCl
Lutz H. Gade. Chem. Eur. J. 2012, 18, 3721-3728
Conclusion
•手性 Au(I)催化的不对称反应最早可追溯到 86年 Ito与 Hayashi的 Adol反应,使用手性二茂铁膦配体。由于 Au(I)配合物为线性配位模型,手性配体与催化剂活性位点距离较远,很难创造合适的手性环境。之后直至2005年手性金催化的反应才开始逐渐发展起来,目前主要的例子多集中于手性双膦配体的双金属催化剂。另外以手性 Phosphoramidite 为代表的单膦配体,手性卡宾配体以及由 Toste提出的手性磷酸阴离子控制的手性Au(I)催化剂也有少数例子。•目前,手性金催化剂的发展还存在很多问题没有解决。例如,同其他金属相比金催化的反应多存在底物较窄的问题。手性双膦配体的双金属催化剂中第二个金属中心所起的作用并不明确。而手性单膦配体及手性卡宾金催化的例子较少且有一部分例子只能得到中等 ee值。其他类型的手性配体也有待开发,如大位阻的手性硫脲类配体等等。
N N
S
t-Bu
t-But-Bu
t-Bu
AuCl
Dan Yang. Synthesis, 2007,16, 2539-2544
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