Post on 08-Feb-2021
Reporter: Ran-Ning Guo
Checker: Lei Shi
Date: 2012/10/09
Literature Report 5
Diazo Compounds and N-Tosylhydrazones:Novel Cross-Coupling Partners in
Transition-Metal-Catalyzed Reactions
Wang, J. et al. Acc. Chem. Res. 2012, DOI: 10.1021/ar300101k
2
Contents
Can cross-coupling and metal carbene transformations bemerged into a single reaction cycle?
How many kinds of transition metals are effective in this cross-coupling reaction?
The perspective of this novel cross-coupling compared with classic ones.
Heck-Mizoroki reaction, Shapiro reaction…
Pd, Cu, Rh, Ni, Co…
Conspectus
Standard Cross-Coupling vs the Coupling Involving a Carbene Process
5
Pd-Catalyzed Cross-Coupling Reaction between Benzyl Halides and TMSCHN2
Van Vranken, D. L. et al. Tetrahedron 2001, 57, 5219–5225
Ar X +SiMe3H
N2
2.5 mol% Pd2(dba)320 mol% AsPh3
2 equiv. iPr2NEtDCE, reflux
Ar
54-60%X = Cl, Br
Pd0
ArPdII
A
PdII
HTMS
Ar
H
Ar HTMS
PdII
HAr
TMSH
PdIIH
B C D
6
N-tosylhydrazones have been proven to be very useful for the in situ generation of nonstabilized diazo compounds through Bamford-Stevens reaction.
N-tosylhydrazones: generate unstable diazo compounds in situ
7
Pd-Catalyzed Cross-Coupling of N-Tosylhydrazones
Barluenga, J. et al. Angew. Chem. Int. Ed. 2007, 46, 5587–5590
8
Pd-Catalyzed Cross-Coupling of Vinylhalides with EDA
Wang, J. et al. J. Am. Chem. Soc. 2007, 129, 8708–8709
9
The Mechanism of Pd-Catalyzed Cross-Coupling of Iodides with EDA
RI R PdII IEDA
CO2EtPdII
N2H
RCO2Et
PdIIR
H
base
PdII
N2
CO2EtR
Pd0
R
N2
CO2Et
A B D
C
Wang, J. et al. J. Am. Chem. Soc. 2007, 129, 8708–8709
10
Pd-Catalyzed Oxidative Cross-Coupling between Boronic Acids and α-Diazocarbonyl Compounds
Wang, J. et al. J. Am. Chem. Soc. 2008, 130, 1566–1567
11
Wang, J. et al. Chem. Commun. 2010, 46, 1724–1726
ArR'
R
NNHTs
+ Ar'B(OH)2
5 mol% Pd(PPh3)410 mol% CuCl, O2
5 equiv. LiOtBudioxane, 70 oC
Ar
Ar'
R'
R28 examples
30-84%
Pd-Catalyzed Oxidative Cross-Coupling between Boronic Acids and N-Tosylhydrazones
12
Pd-Catalyzed Cross-Coupling between Benzylhalides and N-Tosylhydrazones
Wang, J. et al. Org. Lett. 2009, 11, 4732–4735
13
Pd-Catalyzed Cross-Coupling between Benzylhalides and Diazo Compounds
Van Vranken, D. L. et al. Tetrahedron 2005, 61, 6438–6441
Yu, W.-Y. et al. Org. Lett. 2009, 11, 469–472
BrR
N2
OEt
O
iPrNEt2, C6H680 oC, 12 h
R CO2Et
up to 74% yield
Ar1 Br
CO2Me
N2
Ar2 CO2Me
Ar2Ar1
Pd2(dba)3 CHCl3PPh3
Na2CO380 oC, 3 h
Pd2(dba)3 CHCl3AsPh3
E/Z ratio >20:1up to 88% yield
14
Pd-Catalyzed Cross-Coupling of Diazo Compounds with Allylhalides
Wang, J. et al. Chem. Commun. 2008, 4198–4200
15
Pd-Catalyzed Oxidative Cross-Coupling of N-Tosylhydrazones with Terminal Alkynes
Wang, J. et al. Angew. Chem. Int. Ed. 2011, 50, 3510–3514
R'O2CR
N2+ R''
5 mol% Pd(OAc)220 mol% P(2-furyl)3
BQ, iPr2NHPhMe, 80 oC
R'O2C
R''
R
27-71%E:Z >20:1
R
NNHTs
R' + H R''
5 mol% Pd(OAc)220 mol% P(2-furyl)3
BQ, LiOtBu1,4-dioxane, 90 oC
R''
RR'
R
PdII
R'
R''
RR'
PdII
R''
42-83%Z:E >20:1
16
Liang, Y.-M. et al. Chem. Eur. J. 2011, 17, 6918–6921
Migratory Insertion Allenyl Group in Pd-Catalyzed Reaction
17
Migratory Insertion Cyclopropyl Group in Pd-Catalyzed Reaction
Wang, J. et al. Org. Lett. 2012, 14, 922–925
18
Migratory insertion/β-hydroxy elimination sequence in Pd-Catalyzed Reaction
Wang, J. et al. Chem. Commun. 2011, 47, 3622–3624
19
β-Hydrogen Elimination vs Transmetalation
In the catalytic cycle of the cross-coupling reactions described above, the alkyl palladium species, which are formed by migratory insertion, typically undergo β-hydrogen elimination to give rise to the final products with the formation of C=C. However, when the β-hydrogens are not available, it may be possible to undergo a cascade process, such as a transmetalation with an organometallic reagent and subsequent reductive elimination to form two separate C-C in a carbenic center.
20
Pd-Catalyzed Three-Component Cross-Coupling Reaction
Wang, J. et al. J. Am. Chem. Soc. 2010, 132, 13590-23591
21
Pd-Catalyzed Decarboxylation/Migratory Insertion/Reductive Elimination Cascade
Liang, Y.-M. et al. Angew. Chem. Int. Ed. 2012, 51, 1370-1374
22
Pd-Catalyzed Carbonylation/Acyl Migratory Insertion Cascade
ArI + R CO2R'
N2
+ Et3SiH
5 mol% Pd(PPh3)42 equiv. Et3N
CO balloonDCE, 60 oC
Ar
O
CO2R'
R
18 examples43-88%
ArPdIICO
Ar PdII
OAr PdII
O
CO2R'R
O
Ar
CO2R'
PdII
R
Et3SiH
Wang, J. et al. Angew. Chem. Int. Ed. 2010, 49, 1139-1142
23
Pd-Catalyzed Carbonylation Staudinger Cycloaddition: β-Lactam Synthesis
Wang, J. et al. J. Am. Chem. Soc. 2011, 133, 4330–4341ACS Catal. 2011, 1, 1621–1630
24
Pd-Catalyzed Amidation of N-Tosylhydrazones with Isocyanides
NNHTs
Pd0 Pd
N
tBu
C N
tBu
NHtBu
OC N tBu
2 mol% Pd(PPh3)4Cs2CO3
1,4-dioxane-H2O75%
C N tBu
H2O
Ding, K. et al. Chem. Eur. J. 2011, 17, 12268–12271
25
Cu(I)-Catalyzed Coupling of N-Tosylhydrazones with Terminal Alkynes
Wang, J. et al. Angew. Chem. Int. Ed. 2011, 50, 1114–1117
26
Cu-Catalyzed Synthesis of Benzofurans, Indoles, and Phenanthrenes
NNHTs
HAr+
H R
cat. CuI
baseAr
H R
H
Ar =
XH
Ar =
Ph
CuI
R
XH X R
X = O or NH
R R
Wang, J. et al. Org. Lett. 2011, 13, 5020-5023
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The sequence of migratory insertion/protonation from Cu(I) carbene, provides a new possibility for C(sp2)-C(sp3) and C(sp)-C(sp3) single bond formation.
28
Cu-Catalyzed C(sp)-C(sp3) Bond Formation
Wang, J. et al. J. Am. Chem. Soc. 2012, 134, 5742–5745
Cu(I)-Catalyzed Direct Benzylation or Allylation of 1,3-Azoles with N-Tosylhydrazones
N
XH +
NNHTs
R 10 mol% CuI
LiOtBuPhMe or dioxane
110 oC, 1.5 h
N
X
R
X = N, S
48-86%
Wang, J. et al. J. Am. Chem. Soc. 2011, 133, 3296-3299
29
30
Rh(I)-Catalyzed One-Pot Three-Component Reaction
Yu, W.-Y. et al. Org. Lett. 2011, 13, 5370-5373
31
Ni- and Co-Catalyzed Reaction
O
NMe
H +
NNHTs
NiBr2/Phen(10 mol%)
LiOtBu1,4-dioxane100 oC, 8 h
O
NMe
86%
N
OPh H+
NNHTs
LiOtBu1,4-dioxane120 oC, 7 h
CoBr2/Phen(10 mol%)N
OPh
71%
Miura, M. et al. Angew. Chem. Int. Ed. 2012, 51, 775-779
32
Summary-Comparison of Migratory Insertions
33
Summary-Cross-Coupling with Carbonyl: Triflate Approach vs N-Tosylhydrazone Approach
RO
R'
ROTf
R'
cat. Pd0
ArM
RAr
R'
cat. Pd0
ArX
RNNHTs
R'
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Summary-Alkene Synthesis : Shapiro Reaction vs Pd-Catalyzed Cross-Coupling
R'
R R''
NNHTs
nBuLi
R'
R R''
Shapiro reaction
E
R'
R R''
E
E = H, O
LiOtBu or Cs2CO3
R'
R R''
N2
XPdII-E
R'
R R''
PdII E R'
R R''
PdIIE
R'
R R''
E
E = Ar, vinyl, alkynyl, allyl…
35
Summary-Deoxygenative Transformation of Carbonyl Group into C-C or C=C Bonds
36
Thanks!