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Catalytic Hydroamination of Alkynes and Alkenes

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Title: Catalytic Hydroamination of Alkynes and Alkenes


1
Catalytic Hydroamination of Alkynes and Alkenes
  • Zhi-Yong,Han
  • 14.Nov.,2009

2
  1. Introduction
  2. Mechanistic Aspects
  3. Selected Reactions Involving Hydroamination

3
1. Introduction
Problems
slightly exothermic
but
a high reaction barrier
entropically negative
Amines nucleophilic Alkenes and Alkynes
electron rich
strong electron repulsion
4
Number of articles published on
hydroamination Until 2008.3 ,61 review articles
covering many aspects of hydroamination have been
published
alkali and lanthanide
zirconium, titanium, and late transition metal
5
2.1 Rare-Earth Metals Catalysts
Merits highly efficient for intramolecular
hydroamination with very high turnover
frequencies and excellent stereoselectivities
Demerits air and moisture sensitive, and cannot
tolerate acidic substrates
Hong, S. Marks, T. J. Acc. Chem. Res. 2004, 37,
673686.
6
Molander, G. A. Hasegawa, H. Heterocycles 2004,
64, 467474.
Li, Y. Fu, P.-F. Marks, T. J. Organometallics
1994, 13, 439440. Li, Y. Marks, T. J. J. Am.
Chem. Soc. 1996, 118, 92959306.
radius of the rare-earth metal ion?
Catalytic activity ?
Gagne, M. R. Stern, C. L. Marks, T. J. J. Am.
Chem. Soc. 1992, 114, 275294.
7
2.2 Alkaline Earth Metals Catalysts
The chemistry of organometallic alkaline earth
metal complexes is closely related to that of the
rare-earth elements
Buch, F. Harder, S. Z. Naturforsch. 2008, 63b,
169177.
8
2.3 Group 4/5 Metal Based Catalysts
a-elimination
Johnson, J. S. Bergman, R. G. J. Am. Chem. Soc.
2001, 123, 29232924.
9
Substrate affected anti-Markovnikov
Ackermann, L. Organometallics 2003, 22, 43674368.
Beller, M. Angew. Chem., Int. Ed. 2002, 41,
25412543. Beller, M. Chem. Eur. J. 2004, 10,
24092420.
Doye, S. Org. Lett. 2000, 2, 19351937.
Odom, A. L. Org. Lett.2004, 6, 29572960.
10
One pot reaction
Wren, S. L. Organometallics 2003, 22, 43934395.
highly anti-Markovnikov
Schafer, L. L. Org. Lett. 2003, 5, 47334736.
Schafer, L. L.Chem. Eur. J. 2007, 13, 20122022.
Doye, S. Angew. Chem., Int.Ed. 2005, 44,
29512954.
11
2.4 Late Transition Metal Catalysts
Ru(0), Rh(I)/Rh(III), Ir(I)/Ir(III), Pd(II),
Pt(II), Pt(IV), Cu(I), Zn(II), Au(I)/Au(III), Ag(I
), Ni(0), Re(I), Fe(III), Bi(III), and toxic
Cd(II), Hg(II)
Four different categories of mechanism
  1. nucleophilic attack on a coordinated alkene or
    alkyne
  2. nucleophilic attack on allylic complexes
  3. insertion of the alkene/alkyne into a
    metal-hydride bond
  4. oxidative addition of the amine, followed by
    insertion into the metal-amide bond

12
2.4.1 Nucleophilic Attack on Coordinated
Alkene/Alkyne
DFT calculations indicate that group 10 catalysts
preferentially react via path A, while group 9
catalysts are inclined to path B
the rate-determining step of such a catalytic
cycle would be the cleavage of the metal-carbon
bond
Muller, T. E., Organometallics 2000, 19,170183.
13
Catalyst resting state
? represents 23 ? represents 27
The choice of the amine is a critical feature of
hydroamination with late transition metal
complexes.
ratek134k1k233k1k2k32332
k1k2k323k4/23k1k2k3k4
Reaction rates are generally higher, the lower
the basicity of the amine nucleophile is.
Thomas E. Muller,Chem. Rev. 2008, 108, 37953892
Crabtree, R. H. Org. Lett. 2005, 7, 54375440.
14
For alkenes the less basic the amine is, the
faster the reaction proceeds For alkynes more
acidic amine or amide N-H, means less
nucleophilic and slower reaction rate
Tilley, T. D. J. Am. Chem. Soc. 2005, 127,
1264012646. Takemoto, Y.,SYNLETT, 2008, 11,
16471650
15
rhodium-catalyzed, anti-Markovnikov oxidative
amination
a tridentate ligand would block the open
coordination sites required for â-hydride
elimination,
Beller, M. Angew. Chem., Int. Ed. Engl. 1997, 36,
22252227.
Michael, F. E., J. Am. Chem. Soc. 2006, 128,
42464247.
16
2.4.2 Nucleophilic Attack on Allylic Complexes
Yamamoto, Y. J. Am. Chem. Soc. 2004, 126,
16221623. Yamamoto, Y. J. Org. Chem.1999, 64,
45704571.
Yamamoto, Y. Tetrahedron Lett. 1998, 39, 54215424
17
Michael type
Hartwig, J. F. J. Am. Chem. Soc. 2005, 127,
57565757.
Hartwig, J. F. J. Am. Chem. Soc. 2004, 126,
27022703
18
2.4.3 Insertion into the M-H Bond of Metal
Hydrides
Hartwig, J. F. J. Am. Chem. Soc. 2000, 122,
95469547 Muller, T. E. J. Mol. Catal. A. Catal.
2007, available online, doi 10.1016/j.molcata.200
7.06.016.
19
2.4.4 Oxidative Addition
Effective couples
Ru0/RuII,RhI/RhIII, IrI/IrIII, Pt0/PtII, CuI/CuIII
Activation of the amine by oxidative addition to
acoordinatively unsaturated late transition metal
in low oxidation state
Hartwig, J. F. Science 2005, 307, 10801082.
20
3. Selected Reactions Involving Hydroamination
Muller, T. E. Tetrahedron 2001, 57, 60276033.
Muller, T. E.J. Catal. 2004, 221, 302.
Reusable Cat.
Turner, P. Organometallics 2004, 23, 17141721.
21
Mitsudo, T.-A. J. Organomet.Chem. 2001, 622,
149154
Reaction rate Ph gt H gt MegtgtSiR3
Hashmi, A. S. K. Eur. J. Org. Chem. 2006,
49054909.
22
Intermolecular hydroamination of aniline and aryl
or alkynes
Hartung, C. G. Tillack, A. Trauthwein, H.
Beller, M. J. Org. Chem.2001, 66, 63396343.
Liu,X-Y.Che,Z.-M. Org. Lett. 2009, 11, 42044207.
23
Mitsudo, T.-A. J. Organomet.Chem. 2001, 622,
149154.
Messerle, B. A. Organometallics 2000, 19, 8790
Liu, S. T. Organometallics 2007, 26, 10621068.
Muller, T. E.. Organometallics 2000, 19, 170183.
Burling, S. Aust.J. Chem. 2004, 57, 677680.
24
Double Hydroamination
Zhang, Y. Donahue, J. P. Li, C. J. Org. Lett.
2007, 9, 627630.
Sun, L.-P. Huang, X.-H. Dai, W.-M. Tetrahedron
2004, 60, 10983 10992.
25
Isocyanate mediated tandem reaction
Reiko Yanada Angew. Chem., Int. Ed.Engl. 2009,
ASAP.
26
Application of Ynamides
Skrydstrup,T.,Org. Lett., 11, 2009, 221
Ynamides are more reactive than alkynes
Skrydstrup,T.,Org. Lett., 11, 2009, 4208
27
N-H insertion tandem hydroamination
Jian-Bo, Wang, Adv. Synth. Catal. 2008, 350, 2359
2364
28
Hydroamination/Heck reaction sequence
Lutz Ackermann, Chem. Commun. , 2004, 2824
Hydroamination/Oxidation tandem reaction
Ning Jiao, Angew. Chem. Int. Ed. 2009, 48, 4572
4576
29
Intramolecular amide N-H and yne hydromation via
MBase or TBAF
Why double Fluoro substrate were selected? (Vide
infra)
Hammond,G.,B., Org. Lett., 9, 2007, 4251
30
(No Transcript)
31
Re catalyzed cyclic amide N-H yne hydroamination
Rt-Bu, Bn, Alkane No Aryl yne substrates
anti-Markovnikov products only
Takai,K., Org. Lett., 9, 2007, 5609
32
A Rh catlyzed tandem reaction
This product may be reducted by Hantzsh ester
catlyzed by bronsted acid
Fukumoto,Y., Org. Lett., 8, 2006, 4641
33
Hydroamination using ammonia
Bertrand,G.,Angew. Chem. Int. Ed. 2008, 47, 5224
5228
Bertrand,G., J. AM. CHEM. SOC. 2009, 131,
86908696
These gold above catalysts are very robust !
G. Bertrand, Proc. Natl. Acad. Sci. USA 2007,
104, 13569 13573
34
Hydroxyl group assisted hydroamination/hydroarylat
ion tandem
This protocol became less useful after effective
catalysts were found, Maybe less active amide/yne
sbustrates could be used Or design new reactions
than could make the hydroxyl group useful.
Nitin T. Patil, J. Org. Chem. 2009, 74, 63156318
35
Liu, Xin-Yuan, Che, Chi-Ming, Angew. Chem. Int.
Ed. 2009, 48, 2367 2371
Liu, Xin-Yuan, Che, Chi-Ming, Chem. Int. Ed.
2008, 47, 3805 3810.
36
Ru catalyzed amide/alkyne hydroamination reaction
100oC 15h
Lukas J. Goobn, Angew. Chem. Int. Ed. 2005, 44,
4042 4045
37
Ru catalyzed amide/alkyne hydroamination
Question is the catalyst acid-torleratable?
Catalyst formation
Method A 1.00 mmol benzamide, 2.00 mmol
1-hexyne, 5 mol (cod)Ru(met)2, 6 mol dcypb, 4
mol Yb(OTf)3, 3 mL DMF and 108 mL wateras
co-solvent, 60 oC, 6 h. Method B After complete
conversion following method A, 3 molecular
sieves (500 mg) and triethylamine (200 mL) were
added, and the mixture was heated to 1108C for 24
h.
Lukas J. Goossn, Angew. Chem. Int. Ed. 2008, 47,
8492 8495
38
Rh catalyzed Amide/Alkyne hydroamination/oxidation
-coupling tandem
No external alkynes substrates
Keith Fagnou, JACS, 130, 2008, 16474
39
Phthalimide/Activated alkyne hydroamination
oxidation tandem
Nai-Xing Wang, and Jin-Heng Li ,10, 2008, 1179
40
Secondary amine, alkyne and activated alkyne
multicomponent reacton
Chao-Jun,Li, Adv. Synth. Catal. 2008, 350, 2226
2230
41
Copper catalyzed Alkyne, azide and amine or H2O
multicomponent reaction
amidine
Question Can the CN bond in amidine be used in
organocatalyzed reaction?
Sukbok Chang J. AM. CHEM. SOC. ,127, 2005,
16047 Sukbok Chang J. AM. CHEM. SOC. 127 ,2005,
2038
42
Insitu formation of activated alkyne then
hydroamination
Hirokazu Urabe, J. AM. CHEM. SOC. 2008, 130,
1820-1821
43
amide and oxygen activated alkyne hydroamination
reaction
The C-C double bond in the product should be
active for many tandem reactions
Sergey A. Kozmin, Angew. Chem. Int. Ed. 2006, 45,
4991 4993
44
Thanks
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