Reaction Mechanism of Nickel Complex Catalyzed Isomerization of N-Allylamides†

doi:10.7503/cjcu20180117

Abstract

Abstract:

Reaction mechanism of Ni(PPh₃)₂-catalyzed isomerization of N-allylamides to generate N-propenylamides was studied theoretically in detail by using density functional theory(DFT) method. The C—H bond activation, isomerization, and reductive elimination to form new C—H bond steps were involved. For C—H bond activation and isomerization steps, Ni(PPh₃)₂ and Ni(PPh₃) with only one PPh₃ ligand were considered and found that the former was more active than the later for these two steps. Both π-allyl and σ-allyl mechanisms were calculated for isomerization and found that the π-allyl mechanism was preferred kinetically to the σ-allyl one. The rate-determining energy barrier to generate the E isomer of product is 141.8 kJ/mol, close to that of 141.1 kJ/mol to generate the Z isomer, in agreement with the experimental result that E/Z=56/44. Considering Pd(PPh₃)₂ as the catalyst active species, it is found that the rate-determining energy barriers for the formation of E and Z isomers are more than 175 kJ/mol, consistent with the experimental observation that Pd(PPh₃)₄ showed no reactivity. The difference of reactivity between Ni(PPh₃)₂ and Pd(PPh₃)₂ can be understood from the more strong back-donation of d electrons from Ni to π^* anti-bonding orbital of allyl anion comparing with Pd. In addition, the influence of substituents in reactants on E/Z selectivity has been analyzed and found that the steric repulsion between substituents and Ph of PPh₃ in the rate-determining transition states to generate E and Z isomers induces the difference of E/Z selectivity.

Key words: C—H Bond activation;, Alkene isomerization, π-Allyl;, σ-Allyl;, N-Propenylamide

CLC Number:

O641

TrendMD:

FANG Sheng, WANG Meiyan, LIU Jingjing, LIU Jingyao. Reaction Mechanism of Nickel Complex Catalyzed Isomerization of N-Allylamides^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1475.

Figures/Tables 8

Fig.1 Energy profiles calculated for C—H bond activation by Ni(PPh3)2(1Ni) to form complex 3Ni^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.2 Energy profiles calculated for isomerization of π-allyl complex 3Ni via the π-allyl mechanism to generate E isomer^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.3 Energy profiles calculated for isomerization of π-allyl complex 3Ni via the σ-allyl mechanism to generate E isomer^ The H atom bonded to Ni is directed outwards(A) and inwards(B). The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.4 Energy profiles calculated for isomerization of π-allyl complex 3'Ni via the π-allyl(A) and σ-allyl(B) mechanism^ The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.5 Structures and energies of the rate-determining intermediate 2ZNi and five lowest transition states on the energy profiles to generate Z isomer^The calculated free energies relative to 1Ni+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.6 Structures and energies of the rate-determining intermediate 2Pd and transition states TS34aPd and TS34ZaPd on the energy profiles to generate E and Z isomer^The calculated free energies relative to 1Pd+N-allyl-4-methylbenzamide are given in kJ/mol.

Fig.7 Energy decomposition analyses of the energy barriers(kJ/mol) from rate-determining intermediates 2M to transition states TS34aM^ a. The energy of Ni; b. the energy of Pd; c. the energy difference of Ni and Pd.

Fig.8 Structures and energies(kJ/mol) of two rate-determining transition states TS34a-tBu and TS34Za-tBu(A) for reactant with R=tBu (relative to 1Ni+N-allyl-pivaloylamide), as well as TS34a and TS34Za(B) for reactant with R=p-MeC6H4 (relative to 1Ni+N-allyl-4-methylbenzamide)

References 37

[1]	Van Santen R.A.,van Leeuwen P. W. N. M.,Moulijn J A.,Averill B. A., Catalysis: An Integrated Approach, Elsevier,Amsterdam, 1999
[2]	Mirza-Aghayan M., Boukherroub R., Bolourtchian M., Hoseini M., Tabar-Hydar K., J. Organomet. Chem., 2003, 678, 1—4
[3]	Donohoe T. J., O'Riordan T. J. C., Rosa C. P., Angew. Chem. Int. Ed., 2009, 48, 1014—1017
[4]	Krompiec S., Krompiec M., Penczek H., Ignasiak R., Coord. Chem. Rev., 2008, 252, 1819—1841
[5]	Escoubet S., Gastaldi S., Bertrand M.,Eur. J. Org. Chem., 2005, 3855—3873
[6]	Kramer S., Mielby J., Buss K., Kasama T., Kegnæs S., Chem. Cat. Chem., 2017, 9, 2930—2934
[7]	Wu Q., Wang L., Jin R., Kang C., Bian Z., Du Z., Ma X., Guo H., Gao L.,Eur. J. Org. Chem., 2016, 5415—5422
[8]	Kocen A. L., Brookhart M., Daugulis O., Chem. Commun., 2017, 53, 10010—10013
[9]	Zhuo L. G., Yao Z. K., Yu Z. X., Org. Lett., 2013, 15, 4634—4637
[10]	Stille J.K., Becker Y., J. Org. Chem., 1980, 45, 2139—2145
[11]	Sergeyev S. A., Hesse M., Helvetica Chimica Acta, 2003, 86, 750—755
[12]	Yamada H., Sodeoka M., Shibasaki M., J. Org. Chem., 1991, 56, 4569—4574
[13]	Zacuto M. J., Xu F., J. Org. Chem., 2007, 72, 6298—6300
[14]	Krompiec S., Pigulla M., Kuz'nik N., Krompiec M., Marciniec B., Chadyniak D., Kasperczyk J., J. Mol. Cat. A: Chem., 2005, 225, 91—101
[15]	Krompiec S., Pigulla M., Bieg T., Szczepankiewicz W., Kuz'nik N., Krompiec M., Kubicki M., J. Mol. Cat. A: Chem., 2002, 189, 169—185
[16]	Krompiec S., Pigulla M., Szczepankiewicz W., Bieg T., Kuznik N., Leszczynska-Sejda K., Kubicki M., Borowiak T., Tetrahedron Lett., 2001, 42, 7095—7098
[17]	Neugnot B., Cintrat J. C., Rousseau B., Tetrahedron, 2004, 60, 3575—3579
[18]	Nakanishi S., Otsuji Y., Itoh K., Hayashi N., Bull. Chem. Soc. Jpn., 1990, 63, 3595—3600
[19]	Couture A., Deniau E., Grandclaudon P., Lebrun S., Tetrahedron Lett., 1996, 37, 7749—7752
[20]	Naito T., Yuumoto Y., Kiguchi T., Ninomiya I., J. Chem. Soc., Perkin Trans., 1996, 1, 281—288
[21]	Wang L., Liu C., Bai R., Pan Y., Lei A., Chem. Commun., 2013, 49, 7923—7925
[22]	Kozuch S., Shaik S., J. Am. Chem. Soc., 2017, 11, 4075—4086
[23]	Zhang X., Tutkowski B., Oliver A., Helquist P., Wiest O., ACS Catal., 2018, 8, 1740—1747
[24]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Keith T., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision E. 01, Gaussian Inc., Wallingford CT, 2013
[25]	Becke A. D., Phys. Rev.A, 1988, 38, 3098—3100
[26]	Lee C., Yang W., Parr R. G., Phys. Rev. B, 1988, 37, 785—789
[27]	Becke A. D., J. Chem.Phys., 1993, 98, 5648—5652
[28]	Hay P. J., Wadt W. R., J. Chem. Phys., 1985, 82, 270—283
[29]	Hay P. J., Wadt W. R., J. Chem. Phys., 1985, 82, 299—310
[30]	Ehlers A. W., Böhme M., Dapprich S., Gobbi A., Höllwarth A., Jonas V., Köhler K. F., Stegmann R., Veldkamp A., Frenking G., Chem. Phys. Lett., 1993, 208, 111—114
[31]	Fukui K., Acc. Chem.Res., 1981, 14, 363—368
[32]	Zhao Y., Truhlar D. G., J. Chem. Phys., 2006, 125, 194101
[33]	Dolg M., Wedig U., Stoll H., Preuss H., J. Chem.Phys., 1987, 86, 866—872
[34]	Andrae D., Haeussermann U., Dolg M., Stoll H., Preuss H., Theor. Chem. Acc., 1990, 77, 123—141
[35]	Marenich A. V., Cramer C. J., Truhlar D. G., J. Phys. Chem. B, 2009, 113, 6378—6396
[36]	Kozuch S., Shaik S., Acc. Chem. Res., 2011, 44, 101—110
[37]	Xie H., Kuang J., Wang L., Li Y., Huang L., Fan T., Lei Q., Fang W., Organometallics, 2017, 36, 3371—3381