Direct Electrophilic Silylation of Terminal Alkynes

Organic Letters

Volumn 6, Issue 3, 2004, Pages 421-424

  Andreev, Aleksey A ^a   Konshin, Valeri V ^a   Komarov, Nikolai V ^a   Rubin, Michael ^b   Brouwer, Chad ^b   Gevorgyan, Vladimir ^b  

^a KUBAN STATE UNIVERSITY   (Russian Federation)

^b UNIVERSITY OF ILLINOIS AT CHICAGO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; SILANE DERIVATIVE; ZINC;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; SILYLATION;

EID: 1342264145     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036328p     Document Type: Article

References (49)

1. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
2. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
3. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
4. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
5. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
6. For silyl protection of terminal alkynes, see: (a) Green, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 3rd ed.; Wiley: New York, 1999. For directing an addition reaction to internal double or triple bonds in the presence of silyl-protected terminal alkynes, see: (b) Palmer, C. J.; Casida, J. E. Tetrahedron Lett. 1990, 31, 1539. (c) Schmidt, H. M.; Arens, J. F. Recl. Trav. Chim. Pays Bas 1967, 86, 1138. (d) Holmes, A. B.; Raphael, R. A.; Wellard, N. K. Tetrahedron Lett. 1976, 1539. For selective electrophilic attack, see for example: (e) Shi Shun, A. L. K.; Chernick, E. T.; Eisler, S.; Tykwinski, R. P. J. Org. Chem. 2003, 68, 1339-1347. (f) Kawanami, Y.; Katsuki, I.; Yamaguchi, M. Tetrahedron Lett. 1983, 24, 5131. (g) Brikofer, L.; Rittir, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280.
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49. Our ab initio calculations (6-31G*) indicated that 1-trimethylsilyl-1-butyne is ca. 9 kcal/mol more stable than its allenic isomer 1-trimethylsilyl-1,2-butadiene. Thus, even if allenylsilane, a potential kinetic product of the deprotonation of 10, is initially formed, it should undergo complete isomerization to its thermodynamically more stable alkynyl counterpart under the reaction conditions.