Page 935 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Cyclic -diazoketones, which are not available from acyl chlorides, can be 911
prepared by reaction of an enolate equivalent with a sulfonyl azide, in a reaction known
as diazo transfer. 133 Various arenesulfonyl azides 134 and methanesulfonyl azide 135 are SECTION 10.2
used most frequently. Because of the potential explosion hazard of sulfonyl azides, Reactions Involving
Carbenes and Related
safety is a factor in choosing the reagent. 4-Dodecylbenzenesulfonyl azide has been Intermediates
recommended on the basis of relative thermal stability. 136 This reagent has been used
in an Organic Synthesis preparation of 1-diazo-4-phenylbut-3-en-2-one. 137

O 1) LiHMDS O
N
2) CF CO CH CF 2
CH 3 3 2 2 3
3) 4-(C H )-PhSO N ,
12 25
2 3
Et N 81–83%
3
A polymer bound arenesulfonyl azide can be prepared from polystyrene. 138
SO Cl
2
SO N
2 3
NaN 3
1) H 2 SO 4
2) SOCl 2 DMF
)
(CHCH ) (CHCH 2 n (CHCH )
2 n
2 n
This reagent effects diazo transfer in good yield.
O O O O
polymer-SO N
Ph CH 3 2 3 Ph CH 3
Et N
3
N 2 98 %
Several types of compounds can act as the carbon nucleophile in diazo transfer,
including the oxymethylene 139 or dialkylaminomethylene 140 derivatives of the ketone.
These activating substituents are lost during these reactions.

O O
+
RCC CHY + ArSO N RCC N N –
2 3
R′ R′
–
Y = O or NR
2
133
F. W. Bollinger and L. D. Tuma, Synlett, 407 (1996).
134 J. B. Hendrickson and W. A. Wolf, J. Org. Chem., 33, 3610 (1968); J. S. Baum, D. A. Shook,
H. M. L. Davies, and H. D. Smith, Synth. Commun., 17, 1709 (1987); L. Lombardo and L. N. Mander,
Synthesis, 368 (1980).
135
D. F. Taber, R. E. Ruckle, and M. J. Hennessy, J. Org. Chem., 57, 4077 (1986); R. L. Danheiser,
D. S. Casebier, and F. Firooznia, J. Org. Chem., 60, 8341 (1995).
136 L. D. Tuma, Thermochimica Acta, 243, 161 (1994).
137 R. L. Danheiser, R. F. Miller, and R. G. Brisbois, Org. Synth., 73, 134 (1996).
138
G. M. Green, N. P. Peet, and W. A. Metz, J. Org. Chem., 66, 2509 (2001).
139 M. Regitz and G. Heck, Chem. Ber., 97, 1482 (1964); M. Regitz, Angew. Chem. Int. Ed. Engl., 6, 733
(1967).
140
M. Rosenberger, P. Yates, J. B. Hendrickson, and W. Wolf, Tetrahedron Lett., 2285 (1964);
K. B. Wiberg, B. L. Furtek, and L. K. Olli, J. Am. Chem. Soc., 101, 7675 (1979).