重排反应在不对称季碳合成中 的应用 任磊 2010.12.4
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重排反应在不对称季碳合成中 的应用 任磊 2010.12.4. 1. Steglich rearrangement. 2.Semipinacol rearrangement. Steglich rearrangement. W. Steglich, G. Hfle, Tetrahedron Lett. 1970, 11, 4727 – 4730. Vedejs （ 2003 ）. Fu （ 1998 ）. Harald Groger （ 2008 ）. Andrew D. Smith （ 2009 ）. - PowerPoint PPT Presentation
Transcript of 重排反应在不对称季碳合成中 的应用 任磊 2010.12.4
重排反应在不对称季碳合成中 的应用
任磊 2010.12.4
1. Steglich rearrangement
2.Semipinacol rearrangement
NO
O
R2
R1
O
X
X=alkyl,alkoxy
cat *
NO
O
R2
R1
X
O
W. Steglich, G. Hfle, Tetrahedron Lett. 1970, 11, 4727 – 4730.
NO
O
R2
R1
O
X
X=alkyl,alkoxy
cat. DMAP or PPY *
NO
O
R2
R1
X
O
NO
O
R2
R1
O
X
N
N
N
N
O XN
O
R2
R1
O
*
NO
O
R2
R1
X
O
fast reversible slow
Steglich rearrangement
Vedejs （ 2003 ）Fu （ 1998 ）
Takashi Ooi （ 2010 ）Andrew D. Smith （ 2009 ）
N
N
SPh
Harald Groger （ 2008 ）
Gregory C. Fu J. Am. Chem. Soc. 1998, 120, 11532-11533
NO
O
Ar
R
O
X
X=alkyl,alkoxy
2% PPY *
NO
O
R2
R1
X
O
t-amyl alcohol 00CAr=4 -MeO -C6H4
T. Howard Black, J. Org. Chem. 1987,52, 5425-5430Gregory C. Fu Angew. Chem. Int. Ed. 2003, 42, 3921 –3924
X
R1
OOR
OR3
R2X
O
R3
R2
R1
O
OR
CH2Cl2R= CMe2CCl3
(S)-2 (5-10mol%)
Christopher J. Richards O L 2006 4 769-772
NO
O
O
OR
OMe
(R,R)-3 (1mol%)
00CN
O
O
OMe
RO
O
Edwin Vedejs J. AM. CHEM. SOC. 2003, 125, 13368-13369 J. AM. CHEM. SOC. 2006, 128, 925-934
NO
O
R1
O
OR
OMe
t-amyl alcohol 00C
NO
O
OMe
R1RO
O
(R)-4 (1mol%)or 5 (10mol%)
Edwin Vedejs J. AM. CHEM. SOC. 2003, 125, 13368-13369
NR2
R1
OOR
O
NR2
O
R1
O
OR (R)-4 (10mol%)
RT
Edwin Vedejs J. AM. CHEM. SOC. 2003, 125, 13368-13369
OO
ORO
OO
O
OR (R)-4 (10mol%)
RTAr
ArO
O
Ar
O
RO
A B
Edwin Vedejs J. AM. CHEM. SOC. 2009, 131, 14–15
N
R1
O
O Cat (10mol%)
OCHPh2
NO
OCHPh2
EtOAC 00C
R1
O
Yield =82-98% Ee =66-94%
N
R1
OOCH2Ar
O Cat (10mol%)
OCHPh2
NO
OCHPh2
CH2Cl2 -200CAr=1-naphthyl
R1
ArH2CO O
Yield =90-99% Ee = 90 -94%
N
N
SPh
NO
O
O
Me
Cat (32mol%)
NO
O
Me
OCDCl3 250C
Y=80%Ee=63%
Harald Groger Synlett 2008, 663 –666; Synthesis 2009, 4208 – 4218.
Andrew D. Smith Angew. Chem. Int. Ed. 2009, 48, 8914 –8918
NO
O
R1
O
OR
OMe
CH2Cl2 -500CN
O
O
OMe
R1RO
O
(S )-1(10mol%)
Wangbin Zhang J. AM. CHEM. SOC. 2010, 132, 15939–15941
NO
O
Ar
R2
O
OR1
Toluene 4A MS 200C
NO
O
OMe
R2R1O
O Cat (10mol%)
N
N
OR
Ee up to 98%
Takashi Ooi Angew. Chem. Int. Ed. 2010, 49, 5567 –5569
NO
O
tBu
R
O
OCH2CCl3
NO
O
tBu
RCl3CH2CO
O
1d (2mol%)
1,4-dioxane 4A MS 250C
Takashi Ooi Angew. Chem. Int. Ed. 2010, 49, 5567 –5569
Yong Qiang Tu Tetrahedron: Asymmetry 13 (2002) 395–398
Semipinacol rearrangement
O
R1
R2
OH Ti(OiPr)4 20mol%
R-BINOL 50mol% -200C
R1
OH
R2
O
n nn=0,1
Ee up to 61%
R1,R2=Alkyl,Aryl
Yong Qiang Tu Chem. Commun., 2005, 5580–5582
R3
R2 R1
OH
Quinine /Seiectfluor
K2CO3 ,MeCN ,rt R3
R2 CHOR1
Yong-Qiang Tu, Angew. Chem. Int. Ed. 2009, 48, 8572 –8574
OOH
R1R1
R2
R2
(R)-19 or (R)-20 (10mol%)
CCl4.RT or 00C
OR1R1
R2
R2
On n
Pri iPr
iPr
Pri
OO P
O
OX
iPr
iPr
(R)-19 X=H(R)-20 X=Ag
Yong-Qiang Tu Angew. Chem. Int. Ed. 2009, 48, 8572 –8574
Yong-Qiang Tu J. AM. CHEM. SOC. 2009, 131, 14626–14627
HO
R1R1
R2
R2CCl4. 400C
R1R1
R2
R2
n n
O O
R3
R3
O
R3
R3
1 (10mol%) N-Boc-L-PhGly(40mol%)
1
N
NH2
HN
H
H
OH
Barry M. Trost J. Am. Chem. Soc. 2001, 123, 7162-7163
OH
R1
R2O
OO
*O R1
Pd2(dba)3 L
CHCl3
NHO
Ph Ph
HNO
PPh2 Ph2P
LR1=Alkyl,ArylR2 =Alkyl
Yield up to 100% Ee up to 93%
Wagner-Meerwein Shift
NHO
Ph Ph
HNO
PPh2 Ph2P
L
Pd2(dba)3 2.5mol% L 7.5mol% CHCl3PhCO2H 10% NEt3 10%
DCE 4A MS
OH
ORRR
O
ORR
R
Barry M. Trost J. AM. CHEM. SOC. 2006, 128, 6044-6045 J. AM. CHEM. SOC. 2008, 130, 6231–6242
F. Dean Toste J . AM. CHEM. SOC. 2009, 131, 9178–9179
