Page 517 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

498 Scheme 5.1. Electrophilic Sulfur and Selenium Reagents

CHAPTER 5 A. Sulfenylation Reagents
Polar Addition 1 a 2 a 3 b 4 c O
and Elimination
+
Reactions ArSCl RSCl (CH 3 ) 2 S SCH 3 BF 4 – RSC(CH 3 ) 3
(CF 3 CO) 2 O
B. Selenenylation Reagents

5 d 6 d 7 e 8 f 9 g
+
PhSeCl PhSeBr PhSe PF 6 – PhSeO CCF 3 PhSeOSO Ar
2
2
10 h 11 i 12 j 13 k 14 l
PhSeOSO CF 3 PhSeOSO 3 – (PhSe) 2 (PhSe) 2 (PhSe) 2
3
(NH ) S O 8 DDQ PhI(OAc) 2
4 2 2
O
15 m
N SePh
O

a. G. Capozzi, G. Modena, and L. Pasquato, in The Chemistry of Sulphenic Acids and Their Derivatives, S. Patai,
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f. H. J. Reich, J. Org. Chem., 39, 428 (1974).
g. T. G. Back and K. R. Muralidharan, J. Org. Chem., 58, 2781 (1991).
h. S. Murata and T. Suzuki, Tetrahedron Lett., 28, 4297, 4415 (1987).
i. M. Tiecco, L. Testaferri, M. Tingoli, L. Bagnoli, and F. Marini, J. Chem. Soc., Perkin Trans. 1, 1989 (1993).
j. M. Tiecco, L. Testaferri, M. Tingoli, D. Chianelli, and D. Bartoli, Tetrahedron Lett., 30, 1417 (1989).
k. M. Tiecco, L. Testaferri, A. Temperini, L. Bagnoli, F. Marini, and C. Santi, Synlett, 1767 (2001).
l. M. Tingoli, M. Tiecco, L. Testaferri, and A. Temperini, Synth. Commun., 28, 1769 (1998).
m. K. C. Nicolaou, N. A. Petasis, and D. A. Claremon, Tetrahedron, 41, 4835 (1985).

5.4.1. Sulfenylation

By analogy with halogenation, thiiranium ions can be intermediates in
electrophilic sulfenylation. However, the corresponding tetravalent sulfur compounds,
which are called sulfuranes, may also lie on the reaction path. 92

R Cl R Cl –
S S +
C C + RSCl
C C C C

chlorosulfurane thiiranium ion

The sulfur atom is a stereogenic center in both the sulfurane and the thiiranium ion,
and this may influence the stereochemistry of the reactions of stereoisomeric alkenes.
Thiiranium ions can be prepared in various ways, and several have been characterized,
such as the examples below.

92
M. Fachini, V. Lucchini, G. Modena, M. Pasi, and L. Pasquato, J. Am. Chem. Soc., 121, 3944 (1999).