Reaction mechanism for the LiCl-mediated directed zinc insertion: A computational and experimental study

Chemistry - A European Journal

Volumn 16, Issue 6, 2010, Pages 1780-1784

  Liu, Ching Yuan ^a,b   Wang, Xuan ^a   Furuyama, Taniyuki ^a   Yasuike, Shuji ^a,b   Muranaka, Atsuya ^a   Morokuma, Keiji ^c   Uchiyama, Masanobu ^a,b  

^a RIKEN   (Japan)

^b HOKURIKU UNIVERSITY   (Japan)

^c EMORY UNIVERSITY   (United States)

Author keywords

Density functional calculations; Insertion; Lithium chloride; Reaction mechanisms; Regioselectivity; Zinc

Indexed keywords

ARYL ZINC; CL ATOMS; DENSITY-FUNCTIONAL CALCULATIONS; EXPERIMENTAL STUDIES; FUNCTIONALIZED; GENERATION MECHANISM; LITHIUM CHLORIDE; NATURAL BOND ORBITAL ANALYSIS; RATIONAL DESIGN; REACTION MECHANISM; REACTION MECHANISMS; SYNTHETIC TRANSFORMATIONS; ZINC INSERTION;

CHEMICAL BONDS; CHLORINE COMPOUNDS; LITHIUM; REGIOSELECTIVITY;

ZINC;

LITHIUM CHLORIDE; ZINC;

ARTICLE; CATALYSIS; CHEMICAL MODEL; CHEMISTRY; METHODOLOGY;

CATALYSIS; LITHIUM CHLORIDE; MODELS, CHEMICAL; RESEARCH DESIGN; ZINC;

EID: 75749109335     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200902957     Document Type: Article

References (22)

1. a) Handbook of Functionalized Organometallics, Vol.1 (Ed.: P. Knochel), Wiley-VCH. Weinheim. 2005, p 251;
2. b) Organozinc Reagents (Eds.: P. Knochel, P. Jones), Oxford University Press, New York, 1999:
3. c) H. Ren, G. Dunet. P. Mayer, P. Knochel. J. Am. Chem. Soc. 2007, 129. 5376-5377:
4. d) A. Metzger. M. Schade, P. Knochel, Org. Lett. 2008, 10. 1107-1110:
5. e) A. Metzger. M. Schade, G. Manolikakes, P. Knochel, Chem. Asian J. 2008, 3, 1678-1691;
6. f) R.E. Mulvey. F. Mongin. M. Uchiyama, Y. Kondo, Angew. Chem. 2007, 119, 3876-3899;
7. Angew. Chem. Int. Ed. 2007, 46, 3802-3824.
8. A. Krasovskiy. V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem. 2006, 118, 6186-6190:
9. Angew. Chem. Int. Ed. 2006, 45, 6040-6044.
10. N. Boudet, S. Sase, P. Sinha, C.-Y. Liu. A. Krasovskiy, P. Knochel, J. Am. Chem. Soc. 2007, 129, 12358-12359.
11. a)K. Koszinowski, P. Böhrer, Organometallics 2009, 28, 771-779;
12. b)K. Koszinowski, P. Böhrer, Organometallics 2009, 28, 100-110;
13. c) R. Bilow, S. Deuerlein. T. Sley, R. Herbst-Irmer. H. Gornitzka, D. Stalke. Z. Naturforsch. B 2004, 59, 1471-1479.
14. The basis set denoted 631SVP consists of Ahlrichs' SVP all-electron basis set for the zinc and bromine aloms and 6-31 + G* for the other atoms. For details of theoretical methods and chemical models, see: a) F. E. Hæffner, C. Sun, P. G. Williard, J. Am. Chem. Soc. 2000, 122, 12542-12546;
15. b) M. Uchiyama, S. Nakamura, T. Ohwada, M. Nakamura, E. Nakamura, J. Am. Chem. Soc. 2004, 126, 10897-10903;
16. c) M. Uchiyama, Y. Matsumoto, S. Usui, Y. Hashimoto, K. Morokuma, Angew. Chem. 2007, 119, 944-947;
17. Angew. Chem. Int. Ed. 2007, 46, 926-929.
18. a) K. Fukui, Acc. Chem. Res. 1981, 14, 363-368;
19. b) K. Ishida, K. Morokuma, A. Komornicki, J. Chem. Phys. 1977, 66, 2153-2156.
20. NPA, NRT and NBO analysis were carried out by using NBO 3.0 program on Gaussian 03. NBO analysis was performed using "CHOOSE" keywords in order to standardize the resonance structure representations of each TS. The details are given in the Supporting Information; Gaussian 03 (Revision E.01), M.J. Frisch. G.W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven, K. N. Kudin, J.C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi. G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M.. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 2004.
21. 3, -CN) bromobenzenes were also carried out to study the influence of different functional groups and the effect of LiCl on the substrate reactivity and regioselectivity (see the Supporting Information, TP2, Table S2, for details).
22. -1 ) are as follows: TS5, 15.1, 13.6; TS6, 21.0, 20.4; TS9, 22.1, 20.0; TS10, 24.2, 25.0; TS13, 18.7, 17.6; TS14, 21,4, 20.2, respectively. These calculations do not change the conclusions of the above analysis.