Page 257 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements
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6.13 MARTIN SULFURANE 237
REVIEW PROBLEM 6.18
Write out mechanisms for the reactions involved in the synthesis of Martin sulfurane,
reaction 6.111.
The mechanism of action of Martin sulfurane is shown below for the dehydration of
cyclohexanol:
H
O
R F
O Ph
− Ph
Ph − 2 HOR F (6.112)
S + + O S
Ph +
O
R F
As with SF and related reagents, the alcohol coordinates to the tetravalent sulfur center,
4
followed by stepwise departure of two R OH molecules. In the mechanism proposed below,
F
departure of the second R OH also results in the alkene product:
F
R F R F
O O
H H −
Ph Ph
O S O S
Ph + Ph
O O
R
R F F
Ph
Ph Ph
O S Ph
− R OH − R OH −
F
F
+ O S
O R F +
H
(6.113)
