Catalytic hydroamination of alkynes and alkenes
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Catalytic Hydroamination of Alkynes and Alkenes. Zhi-Yong,Han 14.Nov.,2009. Introduction Mechanistic Aspects Selected Reactions Involving Hydroamination. 1. Introduction. Problems:. slightly exothermic. but. a high reaction barrier. entropically negative. Amines: nucleophilic

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Catalytic Hydroamination of Alkynes and Alkenes

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Catalytic hydroamination of alkynes and alkenes

Catalytic Hydroamination of Alkynes and Alkenes

Zhi-Yong,Han

14.Nov.,2009


Catalytic hydroamination of alkynes and alkenes

  • Introduction

  • Mechanistic Aspects

  • Selected Reactions Involving Hydroamination


Catalytic hydroamination of alkynes and alkenes

1. Introduction

Problems:

slightly exothermic

but

a high reaction barrier

entropically negative

Amines: nucleophilic

Alkenes and Alkynes: electron rich

strong electron repulsion


Catalytic hydroamination of alkynes and alkenes

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


Catalytic hydroamination of alkynes and alkenes

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, 673–686.


Catalytic hydroamination of alkynes and alkenes

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.


Catalytic hydroamination of alkynes and alkenes

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.


Catalytic hydroamination of alkynes and alkenes

2.3 Group 4/5 Metal Based Catalysts

α-elimination

Johnson, J. S.; Bergman, R. G. J. Am. Chem. Soc. 2001, 123, 2923–2924.


Catalytic hydroamination of alkynes and alkenes

Substrate affected anti-Markovnikov

Ackermann, L. Organometallics 2003, 22, 4367–4368.

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.

Odom, A. L. Org. Lett.2004, 6, 2957–2960.


Catalytic hydroamination of alkynes and alkenes

One pot reaction

Wren, S. L. Organometallics 2003, 22, 4393–4395.

highlyanti-Markovnikov

Schafer, L. L. Org. Lett. 2003, 5, 4733–4736.

Schafer, L. L.Chem. Eur. J. 2007, 13, 2012–2022.

Doye, S. Angew. Chem., Int.Ed. 2005, 44, 2951–2954.


Catalytic hydroamination of alkynes and alkenes

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

  • nucleophilic attack on a coordinated alkene or alkyne

  • nucleophilic attack on allylic complexes

  • insertion of the alkene/alkyne into a metal-hydride bond

  • oxidative addition of the amine, followed by insertion into the metal-amide bond


Catalytic hydroamination of alkynes and alkenes

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, 19,170–183.


Catalytic hydroamination of alkynes and alkenes

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

Crabtree, R. H. Org. Lett. 2005, 7, 5437–5440.


Catalytic hydroamination of alkynes and alkenes

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


Catalytic hydroamination of alkynes and alkenes

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, 2225–2227.

Michael, F. E., J. Am. Chem. Soc. 2006, 128, 4246–4247.


Catalytic hydroamination of alkynes and alkenes

2.4.2 Nucleophilic Attack on Allylic Complexes

Yamamoto, Y. J. Am. Chem. Soc. 2004,

126, 1622–1623.

Yamamoto, Y. J. Org. Chem.1999, 64, 4570–4571.

Yamamoto, Y. Tetrahedron Lett. 1998, 39, 5421–5424


Catalytic hydroamination of alkynes and alkenes

Michael type

Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 5756–5757.

Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 2702–2703


Catalytic hydroamination of alkynes and alkenes

2.4.3 Insertion into the M-H Bond of Metal Hydrides

Hartwig, J. F. J. Am. Chem. Soc. 2000, 122, 9546–9547

Muller, T. E. J. Mol. Catal. A. Catal. 2007, available online, doi: 10.1016/j.molcata.2007.06.016.


Catalytic hydroamination of alkynes and alkenes

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, 1080–1082.


Catalytic hydroamination of alkynes and alkenes

3. Selected Reactions Involving Hydroamination

Muller, T. E. Tetrahedron 2001, 57, 6027–6033.

Muller, T. E.;J. Catal. 2004, 221, 302.

Reusable Cat.

Turner, P. Organometallics 2004, 23, 1714–1721.


Catalytic hydroamination of alkynes and alkenes

Mitsudo, T.-A. J. Organomet.Chem. 2001, 622, 149–154

Reaction rate: Ph > H > Me>>SiR3

Hashmi, A. S. K.; Eur. J. Org. Chem. 2006, 4905–4909.


Catalytic hydroamination of alkynes and alkenes

Intermolecular hydroamination of aniline and aryl or alkynes

Hartung, C. G.; Tillack, A.; Trauthwein, H.; Beller, M. J. Org. Chem.2001, 66, 6339–6343.

Liu,X-Y.Che,Z.-M. Org. Lett. 2009, 11, 4204–4207.


Catalytic hydroamination of alkynes and alkenes

Mitsudo, T.-A. J. Organomet.Chem. 2001, 622, 149–154.

Messerle, B. A. Organometallics 2000, 19, 87–90

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.


Catalytic hydroamination of alkynes and alkenes

Double Hydroamination

Sun, L.-P.; Huang, X.-H.; Dai, W.-M. Tetrahedron 2004, 60, 10983–

10992.

Zhang, Y.; Donahue, J. P.; Li, C.

J. Org. Lett. 2007, 9, 627–630.


Catalytic hydroamination of alkynes and alkenes

Isocyanate mediated tandem reaction

Reiko Yanada* Angew. Chem., Int. Ed.Engl. 2009, ASAP.


Catalytic hydroamination of alkynes and alkenes

Application of Ynamides

Skrydstrup,T.,Org. Lett., 11, 2009, 221

Ynamides are more reactive than alkynes

Skrydstrup,T.,Org. Lett., 11, 2009, 4208


Catalytic hydroamination of alkynes and alkenes

N-H insertion tandem hydroamination

Jian-Bo, Wang, Adv. Synth. Catal. 2008, 350, 2359 – 2364


Catalytic hydroamination of alkynes and alkenes

Hydroamination/Heck reaction sequence

Lutz Ackermann, Chem. Commun. , 2004, 2824

Hydroamination/Oxidation tandem reaction

Ning Jiao, Angew. Chem. Int. Ed. 2009, 48, 4572 –4576


Catalytic hydroamination of alkynes and alkenes

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


Catalytic hydroamination of alkynes and alkenes

Re catalyzed cyclic amide N-H yne hydroamination

R=t-Bu, Bn, Alkane

No Aryl yne substrates

anti-Markovnikov products only

Takai,K., Org. Lett., 9, 2007, 5609


Catalytic hydroamination of alkynes and alkenes

A Rh catlyzed tandem reaction

This product may be reducted by Hantzsh ester catlyzed by bronsted acid

Fukumoto,Y., Org. Lett., 8, 2006, 4641


Catalytic hydroamination of alkynes and alkenes

Hydroamination using ammonia

Bertrand,G.,Angew. Chem. Int. Ed. 2008, 47, 5224 –5228

Bertrand,G., J. AM. CHEM. SOC.

2009, 131, 8690–8696

These gold above catalysts are very robust !

G. Bertrand, Proc. Natl. Acad. Sci. USA 2007, 104, 13569 – 13573;


Catalytic hydroamination of alkynes and alkenes

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


Catalytic hydroamination of alkynes and alkenes

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.


Catalytic hydroamination of alkynes and alkenes

Ru catalyzed amide/alkyne hydroamination reaction

100oC 15h

Lukas J. Goobn, Angew. Chem. Int. Ed. 2005, 44, 4042 –4045


Catalytic hydroamination of alkynes and alkenes

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


Catalytic hydroamination of alkynes and alkenes

Rh catalyzed Amide/Alkyne hydroamination/oxidation-coupling tandem

No external alkynes substrates

Keith Fagnou, JACS, 130, 2008, 16474


Catalytic hydroamination of alkynes and alkenes

Phthalimide/Activated alkyne hydroamination oxidation tandem

Nai-Xing Wang, and Jin-Heng Li ,10, 2008, 1179


Catalytic hydroamination of alkynes and alkenes

Secondary amine, alkyne and activated alkyne multicomponent reacton

Chao-Jun,Li, Adv. Synth. Catal. 2008, 350, 2226 – 2230


Catalytic hydroamination of alkynes and alkenes

Copper catalyzed Alkyne, azide and amine or H2O multicomponent reaction

amidine

Question: Can the C=N 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


Catalytic hydroamination of alkynes and alkenes

Insitu formation of activated alkyne then hydroamination

Hirokazu Urabe, J. AM. CHEM. SOC. 2008, 130, 1820-1821


Catalytic hydroamination of alkynes and alkenes

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


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