Page 1051 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

Scheme 11.5. (Continued) 1035
O SECTION 11.4

13 m CH 3 (CH 2 ) 5 CH O + C H O CCH CHCO C H CH (CH ) CCHCO C H Free Radical Addition
2 5
3
2 2 5
2 5
2
2 2 5
Reactions
CH CO C H
2 2 5
2
O O
hv
14 n H NCH + H C CH(CH ) CO CH 3 acetone H NC(CH ) CO CH 3 58%
2 2
2
2
2
2 4
2
2
O hv O
15 o + CH O CCH CHCO CH 3 CHCH 2 CO CH 3
3
2
2
2
acetone
O O 90%
CO 2 CH 3
O
16 p hv CH CCH 3
2
CH CCH 3 +
3
O
17 q CH (CO C H ) + H 2 C CH(CH ) CH 3 ROOR (H5C O C) CH(CH ) CH 3
2 2 5 2
2
2 5
2 7
2
2
2
67–85%
CuO
H O CCH(CH ) CH
18 r NCCH CO C H + H C CH(CH ) CH 3 C 2 5 2 2 7 3 75%
2 2 5
2
2 5
2
CN
D. Addition of Thiols and Thioacids
Ph
19 s CH CSH + C H CH CHCH O CH CSCHCH CH O
3
3
2
6 5
O O 90%
)
(PhCO 2 2
20 t CH (CH ) SH + H C CH(CH ) CH 3 CH (CH ) S(CH ) CH 3 68%
3
3
2 3
2 6
2 4
2
2 3
a. W. J. Bailey and S. S. Hirsch, J. Org. Chem., 28, 2894 (1963).
b. R. Neumann, F. de la Vega, and A. Bar-On, J. Org. Chem., 60, 1315 (1995).
c. H. O. House, C.-Y. Chu, W. V. Phillips, T. S. B. Sayer, and C.-C. Yau, J. Org. Chem., 42, 1709 (1977).
d. M. S. Kharasch, E. W. Jensen, and W. H. Urry, J. Am. Chem. Soc., 69, 1100 (1947).
e. M. S. Kharasch and M. Sage, J. Org. Chem., 14, 537 (1949).
f. C. L. Osborn, T. V. Van Auken, and D. J. Trecker, J. Am. Chem. Soc., 90, 5806 (1968).
g. P. D. Klemmensen, H. Kolind-Andersen, H. B. Madsen, and A. Svendsen, J. Org. Chem., 44, 416 (1979).
h. F. Bellesia, L. Forti, F. Ghelfi, and U. M. Pagnoni, Synth. Commun., 27, 961 (1997).
i. M. S. Kharasch, W. H. Urry, and B. M. Kuderna, J. Org. Chem., 14, 248 (1949).
j. E. C. Macias, J. M. G. Molinillo, G. M. Massanet, and F. Rodriguez-Luis, Tetrahedron, 48, 3345 (1992).
k. S. Tsushimoto, S. Sakaguchi, and Y. Ishii, Tetrahedron Lett., 44, 5601 (2003).
l. H.-S. Dang and B. P. Roberts, J. Chem. Soc. Perkin Trans. 1, 67 (1998).
m. T. M. Patrick, Jr., and F. B. Erickson, Org. Synth., IV, 430 (1963).
n. D. Elad and J. Rokach, J. Org. Chem., 29, 1855 (1964).
o I. Rosenthal and D. Elad, J. Org. Chem., 33, 805 (1968).
p. W. Reusch, J. Org. Chem., 27, 1882 (1962).
q. J. C. Allen, J. I. G. Cadogan, B. W. Harris, and D. H. Hey, J. Chem. Soc., 4468 (1962).
r. A. Hajek and J. Malek, Synthesis, 454 (1977).
s. R. Brown, W. E. Jones, and A. R. Pinder, J. Chem. Soc., 2123 (1951).
t. D. W. Grattan, J. M. Locke, and S. R. Wallis, J. Chem. Soc., Perkin Trans. 1, 2264 (1973).
a mercury lamp. Entries 4 to 8 involve additions of tetrahalomethanes. In Entry
4 the ratio of reactants was 1 00 CCl , 0.33 alkene, and 0.02 peroxide. Similar
4
ratios were used in Entries 6 and 7. Entry 5 was done with irradiation from a
mercury lamp. Entry 6 demonstrates the exclusive exo addition of the trichloromethyl
radical and dominant endo abstraction of chlorine. Entry 8 is an example of a
recently developed procedure in which iron powder acts both as an initiator and
catalyst.
Entries 9 to 16 show additions of various carbon radicals. Entry 9 involves
addition of acetaldehyde to a terminal alkene. The reaction was done under mercury