Mechanism of S(N)2 alkylation reactions of lithium organocuprate clusters with alkyl halides and epoxides. Solvent effects, BF3 effects, and trans-diaxial epoxide opening

Journal of the American Chemical Society

Volumn 122, Issue 30, 2000, Pages 7294-7307

  Mori, Seiji ^a,b   Nakamura, Eiichi ^a   Morokuma, Keiji ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b EMORY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; BORANE DERIVATIVE; BORON DERIVATIVE; COPPER DERIVATIVE; CYCLOHEXENE DERIVATIVE; EPOXIDE; FLUORIDE; HALIDE; LITHIUM; LITHIUM DERIVATIVE;

ALKYLATION; ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATION; ENERGY; REACTION ANALYSIS; SOLVATION; STEREOCHEMISTRY;

EID: 0034596340     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0002060     Document Type: Article

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97. Examples: DelMonte, A. J.; Haller, J.; Houk, K. N.; Sharpless, K. B.; Singleton, D. A.; Strassner, T.; Thomas, A. A. J. Am. Chem. Soc. 1997, 119, 9907-9908. Keating, A. E.; Merrigan, S. R.; Singleton, D. A.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3933-3938. Frantz., D. E.; Singleton, D. A.; Snyder, J. P. J. Am. Chem. Soc. 1997, 119, 3383-3384. Frantz, D. E.; Singleton, D. A. J. Am. Chem. Soc. 2000, 122, 3288-3295. Cf.: Czyryca, P.; Paneth, P. J. Org. Chem. 1997, 62, 7305-7309.
98. For solvent coordination numbers vs energetics, see: Rodgers, M. T.; Armentrout, P. B. J. Phys. Chem. A 1997, 101, 1238-1249.
99. The copper atom in lithium organocuprate does not accept any neutral ligand on copper as confirmed by lack of such structures in the Cambridge Crystallographic Database (version 2.3.7, 1998). See also: Power, P. P. Prog, Inorg. Chem. 1991, 39, 75-112. In dimethyl sulfide solution, mere is no evidence for Cu-S coordination. See: Huang, H.; Liang, C. H.; Penner-Hahn, J. E. Angew. Chem., Int. Ed. Engl. 1998, 37. 1564-1566.
100. The copper atom in lithium organocuprate does not accept any neutral ligand on copper as confirmed by lack of such structures in the Cambridge Crystallographic Database (version 2.3.7, 1998). See also: Power, P. P. Prog, Inorg. Chem. 1991, 39, 75-112. In dimethyl sulfide solution, mere is no evidence for Cu-S coordination. See: Huang, H.; Liang, C. H.; Penner-Hahn, J. E. Angew. Chem., Int. Ed. Engl. 1998, 37. 1564-1566.
101. Isaacs, N. S. Physical Organic Chemistry; Longman Scientific & Technical: Essex, UK, 1987; Chapter 7.
102. Cf.: Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Sac. 1995, 117, 10726-10734.
103. For example: Marino, J. P.; de la Pradilla, R. F.; Laborde, E. J. Org. Chem. 1987, 52, 4898-4913.
104. 2S, is sometimes suspected to act as more than just a solvent (which was found here not to be the case).
105. Harder, S.; Boersma, J.; Brandsma, L.; Kanters, J. A.; Duisenberg, A. J. M.; van Lenthe, J. H. Organometallics 1990, 9, 511-516.
106. Nakamura, E.; Nakamura, M.; Miyachi, Y.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 99-106.
107. (a) Hine, J.; Linden, S.-M.; Kanagasabapathy, V. M. J. Am. Chem. Soc. 1985, 107, 1082-1083.
108. (b) Asao, N.; Kii, S.; Hanagawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729-3732.
109. (c) Omoto, K.; Fujimoto, H. J. Org. Chem. 2000, 65, 2464-2471.
110. Energies of these fragments are calculated for singlet, and triplet energies are about 48 kcal/mol higher than those for singlet.
111. The behavior of organocuprate aggregates in solution was recently discussed in a review. See: Nakamura, E.; Mori, S. Angew. Chem. Accepted for publication.
112. 3D pictures and coordinates of the structures in this paper are available at the following: http://WWW.chem.s.u-tokyo.ac.jp/∼cornmon/ Theo/Sn2/title.