Towards Highly Activating Leaving Groups Studies on the Preparation of Some Halogenated Alkyl Sulfonates 英文参考文献.docVIP

Molecules 2002, 7, 601-617 molecules ISSN 1420-3049 Towards Highly Activating Leaving Groups: Studies on the Preparation of Some Halogenated Alkyl Sulfonates ? Thomas Netscher* and Patrick Bohrer Research and Development, Roche Vitamins Ltd, CH-4070 Basel, Switzerland. Tel. (+41) 61 688 6755, Fax (+41) 61 687 2201 * Author to whom correspondence should be addressed; e-mail: scher@ Received: 16 May 2002; in revised form: 13 August 2002 / Accepted: 24 August 2002 / Published: 31 August 2002 ? Dedicated to Professor em. Dr. mult. Dr. h.c. mult. Alois Haas on occasion of his 70th birthday and in acknowledgement of his contributions to fluorine and sulfur chemistry Abstract: The trichloromethylsulfonyl-, dichloromethylsulfonyl-, chlorosulfonyl-, and fluorosulfonyl esters of a neopentyl-type alcohol have been prepared via sulfonylation or sulfinylation followed by oxidation. The preparative usefulness and potential of the transformations are discussed. Keywords: Alkylation reagents, SN2 substitution reactions, steric hindrance, sulfonic esters, sulfur-oxygen bond cleavage. Introduction Nucleophilic substitution reactions at sp -carbon centers are among the most important 3 transformations in organic chemistry. The nucleofugality of leaving groups used in organic synthesis, measured by the rates of solvolysis, covers a range of at least fourteen orders of magnitude [1,2]. Despite this large variety, there is still a need to improve the efficiency of many SN2-type synthetic operations. Since halides used as (soft) alkylating reagents often tend to undergo elimination reactions on treatment with (hard) nucleophiles like e.g. alcoholates, esters of oxo-acids are widely applied alternatives. While moderately reactive phosphate esters play a crucial role in biological systems, alkyl  Molecules 2002, 7 602 (as also alkenyl and aryl) esters of sulfonic acids in particular are ind