Transcript 43. Palladium-catalyzed allylic amination

Palladium-catalyzed allylic amination
Chem. Rev. 1998, 98, 1689
Angew. Chem. Int. Ed. 2008, 47, 4733
Amination of Functionalized Alkenes
Richard D. Connell et al. J. Org. Chem. 1988, 53, 3845
Bystorm S. E. et al. Tetrahedron Letters, 1985, 26, 1749
Kuiling Ding, et al. J. Org. Chem. 2001, 66, 3238
Chiral N-P Ligands
R
Ligand(m
ol%)
Pd(mol%) X
Reaction
tme(h)
Yield(%)
Ee(%)
Ph
1 (2.6)
2.5
CO2Et
31
80
79
Ph
2 (2.6)
2.5
CO2Et
37
93
97
Ph
3 (4.5)
3.0
CO2Et
12
90-95
99
Ph
4 (4.5)
3.0
CO2Et
12
90-95
97
Ph
5 (4.5)
3.0
CO2Et
12
90
99
Ph
6 (3.0)
3.0
CO2Me
1
98
94
Ph
7 (3.0)
3.0
CO2Me
2
93
88
Me
6 (10.0)
3.0
CO2Me
15
93
30
Me
7 (10.0)
3.0
CO2Me
96
87
57
Me
2 (2.0)
1.0
P(O)Ph2
13
84
73
Tamino Hayashi, et al, J. Am. Chem. Soc. 1989, 111, 6301
Togni, A. et al. J. Am. Chem. Soc. 1996, 118, 1031
Helmchen, G., et al.Tetrahedron: Asymmetry 1994, 5, 573.
Trost, B. M. et al. J. Am. Chem. Soc. 1992, 114, 9327.
Trost, B. M. et al. J. Am. Chem. Soc. 1994, 116, 4089.
Trost, B. M. et al. J. Am. Chem. Soc. 1997, 119, 5962.
Paul S. Pregosin, et al. Organometallics 1999, 18, 1207
Lixin Dai, Xuelong Hou, et al. J. Am. Chem. Soc. 2001, 123, 7471
Chiral P-S ligands
Up to 98% ee
Michael C. Willis, et al. Tetrahedron: Asymmetry ,
2003, 14, 705;
J. W. Faller, et al. Org. Lett., 2004, 6, 1301;
J. W. Faller, et al. Org. Lett. 2005, 7, 633.
Carlos CarreteroJ. Org. Chem. 2003, 68, 3679
Chiral phosohine oxides
Yasumasa Hamada, et al. J. Am. Chem. Soc. . 2004, 126, 3690
Yasumasa Hamada, et al. Org. Lett., 2007, 9, 927
Chatt, J.; Heaton, B. T. J. Chem. Soc. A 1968, 2745
Org. Lett., 2010, 12, 872
Andrei Yudin
Proticacid generated during the reaction is the
prerequisite for product isomerization
DBU keeps the reaction under kinetic control, but achieving a high b/l
ratio requires greater discrimination between isomeric allyl palladium
intermediates, which is achieved through ligand control.
J. Am. Chem. Soc. 2005, 127, 17516;
J. Am. Chem. Soc. 2004, 126, 5086;
J. Am. Chem. Soc. 2007, 129, 14172
Giuliana Cardillo, et al. Org. Lett., 2008 10, 2425
Aqueous Ammonia as Nucleophile
Shu, Kobayashi. et al. J. Am. Chem. Soc. 2009, 131, 4200
Amination of Allylic Alcohols
Shyh-Chyun Yang J. Org. Chem. 1999, 64, 5000
Kinetic Resolution of Indolines
Xuelong Hou, et al. Org. Lett., 2009, 11, 1789
Amination of Nonfunctionalized Alkenes
Hegedus, L. S J. Am. Chem. Soc. 1978, 100, 5800
Stahl, S. S. Org. Lett. 2006, 8, 2257.
R1
Proce
dure
Yield%
2
Yield
%
3
Yield
%
4
H
A
-
86
H
B
-
-
60
Ph
A
-
62
-
Me
(Z/E)=(83:17)
A
84
4
Me
(Z/E)=(83:17)
C
96
-
-
Me(E)
B
91
-
-
Me(Z)
D
94
-
-
Beccalli, E. M
Beccalli, E. M. et al; J.Org. Chem. 2004, 69, 5627.
Chem. Rev ,2007, 107 5318
Christina M White
Intramolecular
Using this alternative palladium(II) source having a counterion that is a
much weaker base, 1H NMR analysis at the same 2 h time point
revealed predominant formation of a ð-allylPd complex (ca. 61%) and
no significant formation of product 3a. The addition of an external
acetate source to this ð-allylPd intermediateled to the formation of 3a
with a similar yield and identicaldiastereoselectivity to that observed
under standard catalytic conditions.
Yields decrease over time，which was most likely due to formation of
Pd-H in the oxidative aminopalladation pathway that mediates olefin
isomerization to 2a
J. AM. CHEM. SOC. 2007, 129, 7274
J. AM. CHEM. SOC. 2008, 130, 3316
Intermaolecular
Lewis acid activition
Stoichiometric Studies To Evaluate the Role of (salen)CrCl 2
The combination of Cr catalyst 2 with BQ was uniquely effective at promoting formation of aminated product 7 in 25%
yield with regio- and stereoselectivities similar to those observed under standard catalytic conditions. Consistent with
2/BQ working together to promote functionalization,sterically hindered quinones such as 2,6-dimethyl quinone result in
significantly diminished yieldsThese results suggest that Pd catalyst 1 mediates allylic C-H cleavage, while Cr catalyst 2
and BQ promote functionalization.
J. AM. CHEM. SOC. 2008, 130, 3316
Brønsted Base activition
Lewis acid and Brønsted Base promoting intermolecular
functionalization
J. AM. CHEM. SOC. 2009, 131, 11701
Theaminopalladation/-hydride elimination mechanism
predicts formation of 22a-d2 but not 22b-d2. The observed
formation of nearly equal amounts of products 22a-d2 and
22b-d2, however, argued against the possibility of
aminopalladation/-hydride elimination pathway and in favor
of a mechanism involving aπ-allyl-Pd intermediate.
Org. Lett., 2009, 11, 2707
J. AM. CHEM. SOC. 2010, 132, 11978
Conclusions:
1. All Pd(0)-catalyzed allylic aminations was promoted by chiral phosphines can
not avoid regioselectivity directly. No other kinds of chiral organomoleculars was
used. Most of them need additives and excess substrates(3 eq. of amines or even
more) to prevent bypath product.
2. Most of Pd(ll)-catalyzed allylic aminations need additives to obtain product and
high regioselectivity. Substrates were limited to functionalized amines.Consice
mechanisms needed to be studied.