Page 265 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 3.2. (Continued) 237

21 u O CO 2 H CH 3 I, KF, O O CO 2 CH 3 SECTION 3.2
O CH 3
CH 3 DMF, 25°C O Introduction of
O O CH 3 Functional Groups by
CH 3 O CH 3 18h CH 3 O Nucleophilic Substitution
O CH 3
at Saturated Carbon
84%
CH 3
H. Sulfonate esters
22 v HO ArSO 3
PPh 3 , i-Pr-O 2 CN NCO 2 -i-Pr
CO 2 CH 3 p-toluenesulfonic acid, CO 2 CH 3
N N
(C 2 H 5 ) 3 N
CPh CPh Ar = p-CH 3 C 6 H 5
O O
I. Phosphorus nucleophiles
23 w +
Ph 3 P + BrCH 2 CH 2 OPh Ph 3 PCH 2 CH 2 OPh Br –
O
24 x
[(CH 3 ) 2 CHO] 3 P + CH 3 I [(CH 3 ) 2 CHO] 2 PCH 3 + (CH 3 ) 2 CHI
85 – 90%
J. Sulfur nucleophiles
25 y
NaOH
CH 3 (CH 2 ) 10 CH 2 Br + S C(NH 2 ) 2 CH 3 (CH 2 ) 10 CH 2 SH
H 2 O
80%
26 z
+
–
Na + – SCH 2 CH 2 S Na + BrCH 2 CH 2 Br S S
27 aa
55 – 60%
1) CH 2 I
N S
–
2) (CH 3 ) 3 CO K + N SCH 3 62%
CH 3
CH 3
a. M. S. Newman and S. Otsuka, J. Org. Chem., 23, 797 (1958).
b. B. A. Pawson, H.-C. Cheung, S. Gurbaxani, and G. Saucy, J. Am. Chem. Soc., 92, 336 (1970).
c. J. J. Bloomfield and P. V. Fennessey, Tetrahedron Lett., 2273 (1964).
d. W. P. Reeves and M. L. Bahr, Synthesis, 823 (1976).
e. D. F. Taber, M. Rahimizadeh, and K. K. You, J. Org. Chem., 60, 529 (1995).
f. M. S. Hadley, F. D. King, B. McRitchie, D. H. Turner, and E. A. Watts, J. Med. Chem., 28, 1843 (1985).
g. A. S. Thompson, G. G. Humphrey, A. M. De Marco, D. J. Mathre, and E. J. J. Grabowski, J. Org. Chem., 58, 5886
(1993).
h. P. Liu and D. J. Austin, Tetrahedron Lett., 42, 3153 (2001).
i. R. B. Moffett, Org. Synth., IV, 466 (1963).
j. J. C. Craig and R. J. Young, Org. Synth., V, 88 (1973).
k. R. E. Benson and T. L. Cairns, Org. Synth., IV, 588 (1963).
l. R. N. McDonald and P. A. Schwab, J. Am. Chem. Soc., 85, 4004 (1963).
m. C. H. Heathcock, C. T. White, J. J. Morrison, and D. Van Derveer, J. Org. Chem., 46, 1296 (1981).
n. E. Adler and K. J. Bjorkquist, Acta Chem. Scand., 5, 241 (1951).
o. E. S. West and R. F. Holden, Org. Synth., III, 800 (1955).
p. F. Lopez-Calahorra, B. Ballart, F. Hombrados, and J. Marti, Synth. Commun., 28, 795 (1998).
q. G. N. Vyas and M. N. Shah, Org. Synth., IV, 836 (1963).
r. L. I. Smity and S. McKenzie, Jr., J. Org. Chem., 15, 74 (1950); A. I. Vogel, Practical Organic Chemistry, 3rd Edition,
Wiley, 1956, p. 973.
s. H. D. Durst, Tetrahedron Lett., 2421 (1974).
t. G. G. Moore, T. A. Foglia, and T. J. McGahan, J. Org. Chem., 44, 2425 (1979).
u. C. H. Heathcock, C.-T. White, J. Morrison, and D. VanDerveer, J. Org. Chem., 46, 1296 (1981).
v. N. G. Anderson, D. A. Lust, K. A. Colapret, J. H. Simpson, M. F. Malley, and J. Z. Gougoutas, J. Org. Chem., 61,
7955 (1996).
w. E. E. Schweizer and R. D. Bach, Org. Synth., V, 1145 (1973).
x. A. H. Ford-Moore and B. J. Perry, Org. Synth., IV, 325 (1963).
y. G. G. Urquhart, J. W. Gates, Jr., and P. Conor, Org. Synth, III, 363 (1965).
z. R. G. Gillis and A. B. Lacey, Org. Synth., IV, 396 (1963).
aa. R. Gompper and W. Elser, Org. Synth., V, 780 (1973).