1 catalytic hydroamination of alkynes and alkenes zhi-yong,han 14.nov.,2009
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3
a high reaction barrier
slightly exothermic
but
entropically negative
Amines: nucleophilic
Alkenes and Alkynes: electron richstrong electron repulsion
Problems:
1. Introduction
4
Number of articles published on hydroaminationUntil 2008.3 ,61 review articles covering many aspectsof hydroamination have been published
alkali and lanthanide zirconium, titanium, and late transition metal
5
2.1 Rare-Earth Metals Catalysts
Hong, S.; Marks, T. J. Acc. Chem. Res. 2004, 37, 673–686.
Merits: highly efficient for intramolecular hydroamination with very high turnover frequencies and excellent stereoselectivities Demerits: air and moisture sensitive,and cannot tolerate acidic substrates
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Molander, G. A.; Hasegawa, H. Heterocycles 2004, 64, 467–474.
Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439–440. Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1996, 118, 9295–9306.
radius of the rare-earth metal ion↓
Catalytic activity ↑
Gagne´, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem.Soc. 1992, 114, 275–294.
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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, 169–177.
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2.3 Group 4/5 Metal Based Catalysts
Johnson, J. S.; Bergman, R. G. J. Am. Chem. Soc. 2001, 123, 2923–2924.
α-elimination
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Ackermann, L. Organometallics 2003, 22, 4367–4368.
Odom, A. L. Org. Lett.2004, 6, 2957–2960.
Beller, M. Angew. Chem., Int. Ed. 2002, 41, 2541–2543.Beller, M. Chem. Eur. J. 2004, 10, 2409–2420.
Doye, S. Org. Lett. 2000, 2, 1935–1937.
Substrate affected anti-Markovnikov
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highly anti-Markovnikov
Schafer, L. L. Org. Lett. 2003, 5, 4733–4736. Schafer, L. L.Chem. Eur. J. 2007, 13, 2012–2022.
Wren, S. L. Organometallics 2003, 22, 4393–4395.
One pot reaction
Doye, S. Angew. Chem., Int.Ed. 2005, 44, 2951–2954.
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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
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2.4.1 Nucleophilic Attack on Coordinated Alkene/Alkyne
Muller, T. E., Organometallics 2000, 19,170–183.
the rate-determining step of such a catalytic cycle would be the cleavage of the metal-carbon bond
DFT calculations indicate that group 10 catalysts preferentially react via path A, while group 9 catalysts are inclined to path B
13Crabtree, R. H. Org. Lett. 2005, 7, 5437–5440.
Catalyst resting state○ represents [23]● represents [27]
The choice of the amine is a critical feature of hydroamination with late transition metal complexes.
rate=k1*[34]=k1*k2*[33]=k1*k2*k3*[23][32]= k1*k2*k3*[23]*k4/[23]=k1k2k3k4
Reaction rates are generally higher, the lower the basicity of the amine nucleophile is.
Thomas E. Muller,Chem. Rev. 2008, 108, 3795–3892
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Ar
NH2
+ [Pt(cod)](TfO)2 NHAr
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, 12640–12646.Takemoto, Y.,SYNLETT, 2008, 11, 1647–1650
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rhodium-catalyzed, anti-Markovnikov oxidative amination
Beller, M. Angew. Chem., Int. Ed.Engl. 1997, 36, 2225–2227.
a tridentate ligand would block the open coordination sites required for â-hydride elimination,
Michael, F. E., J. Am. Chem. Soc. 2006, 128, 4246–4247.
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2.4.2 Nucleophilic Attack on Allylic Complexes
Yamamoto, Y. Tetrahedron Lett. 1998, 39, 5421–5424
Yamamoto, Y. J. Am. Chem. Soc. 2004,126, 1622–1623.Yamamoto, Y. J. Org. Chem.1999, 64, 4570–4571.
17Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 2702–2703
Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 5756–5757.
Michael type
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2.4.3 Insertion into the M-H Bond of Metal Hydrides
Hartwig, J. F. J. Am. Chem. Soc. 2000, 122, 9546–9547Muller, T. E. J. Mol. Catal. A. Catal. 2007, available online, doi: 10.1016/j.molcata.2007.06.016.
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2.4.4 Oxidative Addition
Activation of the amine by oxidative addition to acoordinatively unsaturated late transition metal in low oxidation state
Ru0/RuII,RhI/RhIII, IrI/IrIII, Pt0/PtII, CuI/CuIII
Effective couples:
Hartwig, J. F. Science 2005, 307, 1080–1082.
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Muller, T. E. Tetrahedron 2001, 57, 6027–6033.
H2Ntoluene,110oC3.5h, >99%
Cu(C6H6)Cu(OTf)2(1%)
N
H2Ntoluene,110oC0.5h, >99%
Pd(triphos)(OTf)2/10TfOH
N
10%
Muller, T. E.;J. Catal. 2004, 221, 302.
NH2
THF,67oC N
Rh(bim)(CO)2BPh4 75%
Cat.(1.5%) Rh(bpm)(CO)2BPh4 98%
Ir(bim)(CO)2BPh4 98%
Ir(bpm)(CO)2BPh4 98%
Turner, P. Organometallics 2004, 23, 1714–1721.
Ru3(CO)12 110oC 78%
Reusable Cat.
3. Selected Reactions Involving Hydroamination
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NH2
THF,67oC N
Cat.(1.5%)
Ph
Ph
Ru3(CO)12 150oC >99%
RuBr(C3H5)(CO)3 150oC >99%
Ru(cot)(dmfm)2 150oC 83%
[RuCl2(CO)3]2 150oC 93%
Mitsudo, T.-A. J. Organomet.Chem. 2001, 622, 149–154
O
Cl3CNH
Cat. O
NCl3C
AuCl3 20oC 69%
AuP(C6F5)3SbF6 0oC 98%
Hashmi, A. S. K.; Eur. J. Org. Chem. 2006, 4905–4909.
Reaction rate: Ph > H > Me>>SiR3
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Intermolecular hydroamination of aniline and aryl or alkynes
Liu,X-Y.Che,Z.-M. Org. Lett. 2009, 11, 4204–4207.
Hartung, C. G.; Tillack, A.; Trauthwein, H.; Beller, M. J. Org. Chem.2001, 66, 6339–6343.
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Mitsudo, T.-A. J. Organomet.Chem. 2001, 622, 149–154.
NH2
Cat.
NH
cat. temp. yield
Ru3(CO)12 110 54
Rh(N-N)(CO)2BPh455 55
Messerle, B. A. Organometallics 2000, 19, 87–90cat. temp. yield
Pd(Triphos)(OTf)2 40 100Zn(OTf)2 110 34Cu(MeCN)4PF6 82 100NH2
Cat.
NH
Ph Ph
Liu, S. T. Organometallics 2007, 26, 1062–1068.
Muller, T. E.;. Organometallics 2000, 19, 170–183.
Burling, S.; Aust.J. Chem. 2004, 57, 677–680.
cat. temp. yield
Rh(N-N)(CO)2]BPh4 55 23NHAc
Cat.
NAc
NHAc
Cat.
NAc
nBu nBu
Ir(H)(Cl)(C-N-P)CO 110 21
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Double Hydroamination
Zhang, Y.; Donahue, J. P.; Li, C. J. Org. Lett. 2007, 9, 627–630.
Sun, L.-P.; Huang, X.-H.; Dai, W.-M. Tetrahedron 2004, 60, 10983–10992.
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ArNH2 + Ar'CONH2 +
R PhI(OAc)2 Au(cat.)
O
NHAr'ArHN
R
Au
O
NAr'ArN
R
ArNH2 + Ar'CONH2 +
R PhI(OAc)2 Chiral Au(cat.)
O
NHAr'ArHN
R
Chiral Au(cat.)
O
NAr'ArN
R
Reiko Yanada* Angew. Chem., Int. Ed.Engl. 2009, ASAP.
Isocyanate mediated tandem reaction
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Application of Ynamides
Skrydstrup,T.,Org. Lett., 11, 2009, 221
Ynamides are more reactive than alkynes
Skrydstrup,T.,Org. Lett., 11, 2009, 4208
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Hydroamination/Heck reaction sequence
Lutz Ackermann, Chem. Commun. , 2004, 2824
Ning Jiao, Angew. Chem. Int. Ed. 2009, 48, 4572 –4576
Hydroamination/Oxidation tandem reaction
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Intramolecular amide N-H and yne hydromation via M+Base or TBAF
Why double Fluoro substrate were selected? (Vide infra)
Hammond,G.,B., Org. Lett., 9, 2007, 4251
31
Re catalyzed cyclic amide N-H yne hydroamination
R=t-Bu, Bn, AlkaneNo 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
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Hydroamination using ammonia
These gold above catalysts are very robust !
Ph3PAuMe+PhPA <<< Ph3PAuCl/AgOTf << tBuAuCl/AgOTf
Bertrand,G.,Angew. Chem. Int. Ed. 2008, 47, 5224 –5228
G. Bertrand, Proc. Natl. Acad. Sci. USA 2007, 104, 13569 – 13573;
Bertrand,G., J. AM. CHEM. SOC. 2009, 131, 8690–8696
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Hydroxyl group assisted hydroamination/hydroarylation 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, 6315–6318
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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.
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Ru catalyzed amide/alkyne hydroamination reaction
100oC 15h
Lukas J. Goobn, Angew. Chem. Int. Ed. 2005, 44, 4042 –4045
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Ru catalyzed amide/alkyne hydroamination
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 conversionfollowing 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
Catalyst formation
Question: is the catalyst acid-torleratable?
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Rh catalyzed Amide/Alkyne hydroamination/oxidation-coupling tandem
No external alkynes substrates
Keith Fagnou, JACS, 130, 2008, 16474
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Phthalimide/Activated alkyne hydroamination oxidation tandem
Nai-Xing Wang, and Jin-Heng Li ,10, 2008, 1179
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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
Sukbok Chang J. AM. CHEM. SOC. ,127, 2005, 16047Sukbok Chang J. AM. CHEM. SOC. 127 ,2005, 2038
Question: Can the C=N bond in amidine be used in organocatalyzed reaction?
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Insitu formation of activated alkyne then hydroamination
Hirokazu Urabe, J. AM. CHEM. SOC. 2008, 130, 1820-1821
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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