Page 795 - Advanced Organic Chemistry Part B - Reactions & Synthesis

General References 771
PROBLEMS
J. P. Collman, L. S. Hegedus, J. R. Norton, and R. G. Finke, Principles and Applications of Organotransition
Metal Chemistry, University Science Books, Mill Valley, CA, 1987.
H. M. Colquhoun, J. Holton, D. J. Thomson, and M. V. Twigg, New Pathways for Organic Synthesis,
Plenum Press, New York, 1984.
R. M. Crabtree The Organometallic Chemistry of the Transition Metals, Wiley-Interscience, New York,
2005.
S. G. Davies, Organo-Transition Metal Chemistry: Applications in Organic Synthesis, Pergamon Press,
Oxford, 1982.
F. Diederich and P. J. Stang, Metal-Catalyzed Cross-Coupling Reactions, Wiley-VCH, New York, 1998.
J. K. Kochi, Organometallic Mechanisms and Catalysis, Academic Press, New York, 1979.
E. Negishi, Organometallics in Organic Synthesis, Wiley, New York, 1980.
M. Schlosser, ed., Organometallics in Synthesis: A Manual, Wiley, Chichester, 1994.

Organocopper Reactions

G. Posner, An Introduction to Synthesis Using Organocopper Reagents, Wiley-Interscience, New York, 1975.
R. J. K. Taylor, ed., Organocopper Reagents, Oxford University Press, Chichester, 1994.

Organopalladium Reactions
R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, Orlando, FL, 1985.
R. F. Heck, Org. React., 27, 345 (1982).
E. Negishi and A. de Mejeire, eds., Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 1
and 2, Wiley-Interscience, New York, 2002.
J. Tsuji, Palladium Reagents and Catalysts: Innovations in Organic Synthesis, Wiley, New York, 1996.

Problems

(References for these problems will be found on page 1284.)
8.1. Predict the product of the following reactions. Be sure to specify all elements of
regiochemistry and stereochemistry.

(a) CH 3 10 mol % Cu(I) (b) 1) CuBr-S(CH 3 ) 2 , –45°C
H 2 C C + CH 3 CH CH 2 C 2 H 5 MgBr
2) C 6 H 13 C CH
MgBr O
3) I 2
Pd(PPh 3 ) 2 Cl 2 Cu(I)
(c) CH 2 Br (1.6 mol %) (d) HC C
(H 2 C CHCH 2 ) 2 CuMgBr +
CO, THF O –50°C
CH 2 OH O
(f) O
Pd(PPh 3 ) 4 Pd(PPh 3 ) 4
(e) H H (5 mol %) (1 mol %)
CH 3 CH 2 MgBr + C C CH 3 +H 2 C CHCH 2 O 2 CCH 3
I 80°C,
C 6 H 13
O DBU
(g) Cl (h)
+ [CH 3 (CH 2 ) 3 ] 2 CuLi CH 3 O
C CH
+ [(C 2 H 5 ) 2 CuCN]Li 2
C(CH 3 ) 3