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UNIVERSITY OF JYVÄSKYLÄ

β-Hydride Elimination

β
β

α

UNIVERSITY OF JYVÄSKYLÄ β -Hydride Elimination β α Mikko Leskinen Pihko Research Group Literature Seminar 31.1.2012
UNIVERSITY OF JYVÄSKYLÄ β -Hydride Elimination β α Mikko Leskinen Pihko Research Group Literature Seminar 31.1.2012

Mikko Leskinen

Pihko Research Group Literature Seminar

31.1.2012

UNIVERSITY OF JYVÄSKYLÄ

General Trends for β-Hydride

Elimination

OF JYVÄSKYLÄ General Trends for β -Hydride Elimination McMillen, D. F.; Golden, D. M. Ann. Rev.
OF JYVÄSKYLÄ General Trends for β -Hydride Elimination McMillen, D. F.; Golden, D. M. Ann. Rev.
OF JYVÄSKYLÄ General Trends for β -Hydride Elimination McMillen, D. F.; Golden, D. M. Ann. Rev.

McMillen, D. F.; Golden, D. M. Ann. Rev. Phys. Chem. 1982, 33, 493. Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36, 255. Martinho Simöes, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629 Ziegler, T. Pure & Appl. Chem. 1991, 63, 873. (DFT)

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General Trends for β-Hydride

Elimination

OF JYVÄSKYLÄ General Trends for β -Hydride Elimination b -Hydride elimination can occur when: σ -donation
OF JYVÄSKYLÄ General Trends for β -Hydride Elimination b -Hydride elimination can occur when: σ -donation
OF JYVÄSKYLÄ General Trends for β -Hydride Elimination b -Hydride elimination can occur when: σ -donation

b-Hydride elimination can occur when:

-Hydride Elimination b -Hydride elimination can occur when: σ -donation >> π -backbonding σ -Complex •
-Hydride Elimination b -Hydride elimination can occur when: σ -donation >> π -backbonding σ -Complex •
-Hydride Elimination b -Hydride elimination can occur when: σ -donation >> π -backbonding σ -Complex •
-Hydride Elimination b -Hydride elimination can occur when: σ -donation >> π -backbonding σ -Complex •

σ-donation >> π-backbonding

can occur when: σ -donation >> π -backbonding σ -Complex • there exists a site of

σ-Complex

there exists a site of coordinative unsaturation on the metal cis to the alkyl group which corresponds to a site of electronic unsaturation (empty metal orbital).

the M-C-C-H unit can take up a coplanar conformation which brings the β-hydrogen in close enough proximity to the metal to form an agostic interaction.

the metal is electrophilic resulting in an agostic interaction that is primarily electron donative in nature (i.e. σ-donation>>π-backbonding).

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General Trends for β-Hydride

Elimination

σ-Complex
σ-Complex

• β-Hydride elimination is much more rapid for d 2 and higher metals than for d 0.

In general, the higher the electronegativity of metal, the higher rate of β-hydride elimination.

That is because agostic interaction with a β-C-H bond is stronger for more electronegative metals, as the main impact into this agostic interaction is σ-donation of C-H bond.

Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109. Crabtree, R. H. The Organometallic Chemistry of the Transition Metals 4th Ed. 2005, Wiley

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Agostic Interaction

UNIVERSITY OF JYVÄSKYLÄ Agostic Interaction Prout, K. et al., J. Chem. Soc. Chem. Commun. 1982 ,
UNIVERSITY OF JYVÄSKYLÄ Agostic Interaction Prout, K. et al., J. Chem. Soc. Chem. Commun. 1982 ,
UNIVERSITY OF JYVÄSKYLÄ Agostic Interaction Prout, K. et al., J. Chem. Soc. Chem. Commun. 1982 ,

Prout, K. et al., J. Chem. Soc. Chem. Commun. 1982, 802.

Original definition: “to refer specifically to situations in which a hydrogen atom is covalentlybonded to both a carbon and to a transition metal atom.” Brookhart, M.; Green, M. L. H. J. Organometall. Chem. 1983, 250, 395.

Redefined definition : “distortion of an organometallic moiety which brings an appended C-H bond into close proximity with the metal center.” Scherer, W.; McGrady, G. S. Angew. Chem., Int. Ed. Engl. 2004, 43, 1782.

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Agostic Interaction

Conclusive Evidence: Neutron diffraction Studies

Interaction Conclusive Evidence: Neutron diffraction Studies showing “ aliphatic H atom [H(IA)] occupying a

showing “

aliphatic H atom [H(IA)] occupying a coordination site. The C1-H1 distance of

1.164 Å (3) is the longest such separation ever observed in a crystalline complex.”

the distorted octahedral coordination around the Fe atom with the

Harlow, R. L. et al., J. Am. Chem. Soc. 1980, 102, 981.

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Agostic Interaction: Computational

Studies

OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Morokuma, K. et al., J. Am. Chem. Soc. 1985 ,

Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109.

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Agostic Interaction: Computational

Studies

OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Computational studies suggest that the higher energy of the
OF JYVÄSKYLÄ Agostic Interaction: Computational Studies Computational studies suggest that the higher energy of the

Computational studies suggest that the higher energy of the Ni(II) vacant d orbital (0.1069 hartree) with respect to that of the analogous Pd(II) complex (0.0505 hartree) results in a weaker donative agostic interaction with the βCH σ bond. The energetically optimized geometries of the agostic complexes show a greater lengthening of the βC-H bond in the Pd(II) complex than in the Ni(II) complex, indicative of greater σ-donation in the former. These computational results are consistent the experimentally observed greater stability of Ni alkyls towards β-hydride elimination that Pd alkyls

and can be rationalized based on the greater electronegativity of Pd(II) vs Ni(II) as reflected in their

respective second ionization potentials.

Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109.

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Kinetics

UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see
UNIVERSITY OF JYVÄSKYLÄ Kinetics • Only if the elimination itself is rate limiting we will see

Only if the elimination itself is rate limiting we will see a kinetic isotopic effect for elimination of H over D.

When hydrogens and deuteriums can be competitively abstracted, isotope effects ranging from 2 to 4 are seen.

Ligand loss is often rate determing for β-hydride elimination (but not always).

There must also be an empty orbital ready to accept the pair of electrons that constitutes the β-C-H bond.

A. Yamamoto et al., J. Organomet. Chem. 1976, 120, 257.

B. D. L. Reger and E. C. Culbertson, J. Am. Chem. Soc. 1976, 98, 2789.

Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry

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Stereochemistry of β-Hydride

Elimination

OF JYVÄSKYLÄ Stereochemistry of β -Hydride Elimination • Metalladibutyl and – cycloheptane: The

Metalladibutyl and cycloheptane: The M−C−C−H unit can take up a roughly coplanar conformation which brings the β-hydrogen close to the metal

Metallacyclopentane: The β-hydrogen cannot achieve a synperiplanar

arrangement with the metal, and the elimination is greatly retared

G. M. Whitesides et al., J. Am. Chem. Soc. 1972, 94, 5258. Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry

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Control of β-Hydride Elimination: No β-

Hydride

Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that
Control of β -Hydride Elimination: No β - Hydride • The alkyl is oriented so that

The alkyl is oriented so that the beta position cannot access the metal center (steric bulk or rigidity).

The alkyl would give an unstable alkene as the product.

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Control of β-Hydride Elimination:

Occupying the free coordination site.

-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the
-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the
-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the
-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the
-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the
-Hydride Elimination: Occupying the free coordination site. • β -hydrogen elimination is inhibited by rendering the

• β-hydrogen elimination is inhibited by rendering the intermediate metal complex four-coordinate, which prevents the generation of open coordination sites necessary for β-hydrogen elimination.

Whitesides, G. M.; Gaasch, J. F.; Stedronsky, E. R. J. Am. Chem. Soc. 1972, 94, 5258.

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Control of β-Hydride Elimination:

Occupying the free coordination site.

-Hydride Elimination: Occupying the free coordination site. Hamann, B. C.; Hartwig, J. F. J. Am. Chem.

Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1997 119, 12382.

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Control of β-Hydride Elimination:

Occupying the free coordination site.

-Hydride Elimination: Occupying the free coordination site. • Excess of Br-ligand inhibits the reaction by quenching

Excess of Br-ligand inhibits the reaction by quenching the open site.

Z. Wang and X. Lu, J. Org. Chem. 1996, 61, 2254.

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Smart Ways to Take Advantage of β-

Hydride Elimination: The Asymmetric Heck Reaction

of β - Hydride Elimination: The Asymmetric Heck Reaction Loiseleur, O.; Meier, P.; Pfaltz, A. Angew.
of β - Hydride Elimination: The Asymmetric Heck Reaction Loiseleur, O.; Meier, P.; Pfaltz, A. Angew.

Loiseleur, O.; Meier, P.; Pfaltz, A. Angew. Chem. Int. Ed. Engl. 1996, 35, 200.

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Smart Ways to Take Advantage of β-

Hydride Elimination: The Asymmetric Heck Reaction

of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we
of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we
of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we
of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we
of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we
of β - Hydride Elimination: The Asymmetric Heck Reaction • Here’s the innovative logic: If we

Here’s the innovative logic: If we use a cyclic olefin, we isomerize the bond. This Means we aren’t making a C-C bond between to sp 2 -hybridized bonds, we are making a sp 2 -sp 3 bond. And sp 3 center can be chiral.

Loiseleur, O.; Meier, P.; Pfaltz, A. Angew. Chem. Int. Ed. Engl. 1996, 35, 200.

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Smart Ways to Take Advantage of β- Hydride Elimination: β-Arylation

Take Advantage of β - Hydride Elimination: β -Arylation Renaudat, A.; Jean-Gérard, L.; Jazzar, R.; Kefalidis,

Renaudat, A.; Jean-Gérard, L.; Jazzar, R.; Kefalidis, C. E.; Clot, E.; Baudoin, O. Angew. Chem. Int. Ed. 2010, 49, 7261. Larini, P.; Kefalidis, C. E.; Jazzar, R.; Renaudat,A.; Clot, E.; Baudoin, O. Chem. Eur. J. 2012, ASAP.

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Smart Ways to Take Advantage of β- Hydride Elimination: β-Arylation

Take Advantage of β - Hydride Elimination: β -Arylation Renaudat, A.; Jean-Gérard, L.; Jazzar, R.; Kefalidis,
Take Advantage of β - Hydride Elimination: β -Arylation Renaudat, A.; Jean-Gérard, L.; Jazzar, R.; Kefalidis,

Renaudat, A.; Jean-Gérard, L.; Jazzar, R.; Kefalidis, C. E.; Clot, E.; Baudoin, O. Angew. Chem. Int. Ed. 2010, 49, 7261. Larini, P.; Kefalidis, C. E.; Jazzar, R.; Renaudat,A.; Clot, E.; Baudoin, O. Chem. Eur. J. 2012, ASAP.

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Smart Ways to Take Advantage of β-

Hydride Elimination: Dehydrogenative Diels-Alder

of β - Hydride Elimination: Dehydrogenative Diels-Alder • The First dehydrogenative Diels-Alder Stang, E. M.;

The First dehydrogenative Diels-Alder

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

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Smart Ways to Take Advantage of β-

Hydride Elimination: Dehydrogenative Diels-Alder

of β - Hydride Elimination: Dehydrogenative Diels-Alder Stang, E. M.; White, C. M. J. Am. Chem.
of β - Hydride Elimination: Dehydrogenative Diels-Alder Stang, E. M.; White, C. M. J. Am. Chem.
of β - Hydride Elimination: Dehydrogenative Diels-Alder Stang, E. M.; White, C. M. J. Am. Chem.

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

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Smart Ways to Take Advantage of β-

Hydride Elimination: Dehydrogenative Diels-Alder

of β - Hydride Elimination: Dehydrogenative Diels-Alder Stang, E. M.; White, C. M. J. Am. Chem.

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

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Conclusions

The use of a coordinating ligand (co-catalyst) may prevent the formation of vacant coordination sites

nessecary for β - hydride elimination.

Control of β - hydride elimination will make the transition metal-catalyzed reactions more diversified.