Page 778 - Advanced Organic Chemistry Part B - Reactions & Synthesis

754 Scheme 8.15. (Continued)

CHAPTER 8 a. T. Ishiyama, H. Kizaki, T. Hayashi, A. Suzuki, and N. Miyaura, J. Org. Chem., 63, 4726 (1998).
b. W. F. Goure, M. E. Wright, P. D. Davis, S. S. Labadie, and J. K. Stille, J. Am. Chem. Soc., 106, 6417 (1984).
Reactions Involving c. F. K. Sheffy, J. P. Godschalx, and J. K. Stille, J. Am. Chem. Soc., 106, 4833 (1984).
Transition Metals d. S. R. Angle, J. M. Fervig, S. D. Knight, R. W. Marquis, Jr., and L. E. Overman, J. Am. Chem. Soc., 115, 3966 (1993).
e. S. Cacchi and A. Lupi, Tetrahedron Lett., 33, 3939 (1992).
f. U. Gerlach and T. Wollmann, Tetrahedron Lett., 33, 5499 (1992).
g. B. B. Snider, N. H. Vo, and S. V. O’Neill, J. Org. Chem., 63, 4732 (1998).
h. S. K. Thompson and C. H. Heathcock, J. Org. Chem., 55, 3004 (1990).
i. A. B. Smith III, G. A. Sulikowski, M. M. Sulikowski, and K. Fujimoto, J. Am. Chem. Soc., 114, 2567 (1992).
j. E. Morea and G. Ortar, Tetrahedron Lett., 39, 2835 (1998).

) Cl
I Pd(PPh 3 2 2 CH O C
5 mol %, 3 2
3 equiv TlOAc
O N N
CO, CH 3 OH
Ph
CH 2 Ph 86% Ref. 253
CH 2
It can also be done by in situ generation of other types of electrophiles. For example,
good yields of N-acyl -amino acids are formed in a process in which an amide and
aldehyde combine to generate a carbinolamide and, presumably, an acyliminium ion.
The organopalladium intermediate is then carbonylated prior to reaction with water. 254

Pd(PPh ) Br 2
3 2
LiBr, CO
RCH O + CH 3 CONH 2 RCHCO H
2
NMP
NHCOCH 3
Scheme 8.15 gives some examples of carbonylations and acylations involving
stannane reagents. Entry 1 illustrates synthesis of diaryl ketones from aryl halides and
arylboronic acids. Entries 2 and 3 use stannanes as the nucleophilic reactant. Entry 4
was carried out as part of the synthesis of the Strychnos alkaloid akuammicine. The
triazinone ring serves to protect the aromatic amino group. Entries 5 and 6 introduce
carboxy groups using vinyl and aryl triflates, respectively. Entries 8 and 9 are similar
reactions carried out during the course of multistage syntheses. Entry 10 illustrates
direct formation of an amide by carbonylation.

8.3. Reactions Involving Other Transition Metals

8.3.1. Organonickel Compounds
The early synthetic processes using organonickel compounds involved the
coupling of allylic halides, which react with nickel carbonyl, Ni CO , to give
4
-allyl complexes. These complexes react with a variety of halides to give coupling
products. 255
253 R. Grigg, P. Kennewall, and A. J. Teasdale, Tetrahedron Lett., 33, 7789 (1992).
254 M. Beller, M. Eckert, F. M. Vollmuller, S. Bogdanovic, and H. Geissler, Angew. Chem. Int. Ed.
Engl., 36, 1494 (1997); M. Beller, W. A. Maradi, M. Eckert, and H. Neumann, Tetrahedron Lett., 40,
4523 (1999).
255
M. F. Semmelhack, Org. React., 19, 115 (1972).