Methanesulfonyl Chloride-Dimethylaminopyridine


[124-63-0]  · CH3ClO2S  · Methanesulfonyl Chloride-Dimethylaminopyridine  · (MW 114.56) (DMAP)

[1122-58-3]  · C7H10N2  · Methanesulfonyl Chloride-Dimethylaminopyridine  · (MW 122.19)

(conversion of alcohols to alkenes1)

Alternate Name: Furukawa's reagent.

Physical Data: see Methanesulfonyl Chloride and 4-Dimethylaminopyridine.

Preparative Method: MsCl (2.5 equiv), DMAP (1.25 equiv), H2O (1 equiv), and CH2Cl2 are stirred at rt for 2-3 d.

Handling, Storage, and Precautions: effective even after 6 months; for handling the components, see Methanesulfonyl Chloride and 4-Dimethylaminopyridine.

Conversion of Alcohols to Alkenes.

Furukawa and co-workers found that treatment of alcohols with MsCl/DMAP/H2O/CH2Cl2 (Furukawa's reagent) produces the dehydrated products in good yields (eq 1).1 In the absence of water, the dehydrated products can still be formed, but in very poor yield. Some examples of secondary alcohols undergoing this elimination have also been reported (eq 2).2

Yodav and co-workers reported that treatment of a variety of tertiary alcohols with methanesulfonyl chloride in the presence of DMAP and Triethylamine produces the dehydrated products (eq 3).3 Acid-sensitive functionalities are not affected by the reaction conditions.

Mixtures of internal and terminal and cis- and trans-alkenes are formed in all cases. The reaction can be run at rt or below. For compounds with acid-sensitive groups, this method offers advantages over the use of other reagents used to effect this transformation.

Mesylate Formation.

Treatment of a secondary alcohol with methanesulfonyl chloride in the presence of DMAP yields the corresponding mesylate in good yield (eq 4).4

1. (a) Furukawa, J.; Morisaki, N.; Kobayashi, H.; Iwasaki, S.; Nozoe, S.; Okuda, S. CPB 1985, 33, 440. (b) Fieser, M.; Smith, J. G. FF 1986, 13, 176.
2. (a) Comins, D. L.; Hong, H.; Salvador, J. M. JOC 1991, 56, 7197. (b) Comins, D. L.; Al-awar, R. S. JOC 1992, 57, 4098.
3. Yodav, J. S.; Mysorekar, S. V. SC 1989, 19, 1057.
4. Takahashi, M.; Uchino, T.; Ohno, K.; Tamura, Y. JOC 1983, 48, 4241.

Valerie Vaillancourt & Michele M. Cudahy

The Upjohn Co., Kalamazoo, MI, USA

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