Anchimerically assisted redox reactions : Comparisons of the effect of transannular - OH and -NH2 group son the rate of the aqueous I2 oxidation of thioethers. Structures of the heteroatom bridged l-thioniabicyclo[3.3.1]nonane intermediates
✍ Scribed by Albert A. Hirschon; Marilyn M. Olmstead; Joyce Takahashi Doi; W.Kenneth Musker
- Book ID
- 104220319
- Publisher
- Elsevier Science
- Year
- 1982
- Tongue
- French
- Weight
- 232 KB
- Volume
- 23
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Sumnary*
The rate law for the aqueous I oxidation of 5-amino-1-thiacyclooctane has been determined and compared with 5-hydroxy-1-tglacyclooctane
The crystal structures of the 9-azaand 9-oxa-1-thlonlablcyclo[3.3.l]nonanes formed on oxidative cyclization are compared We recently reported the first X-ray crystal structure determination of an alkoxysulfonium salt, 9-oxa-1-thlonlablcyclo[3.3.l]nonane tnlodlde 1 This salt is formed by oxldatlve cycllzatlon of 5-hydroxy-1-thlacyclooctane, A, using buffered aqueous I, We have now confirmed that the analogous amine derivative, 5-amino-1-thlacyclooctane, I&* undergoes rapid oxidatlve cycllza-TABLE I. Table of Bond Distances (ii) and Angles for (SNC,HI,)(I,). 1(1)-I(2) 2.935(3) C(4)-C(5) 1 53(4) s-C(l)-C(2) 112.12) 1(2)-I(3) 2.903(3) C(5)-C(6) 1.53(5) S-C(7)-C(6) 116.(2) S-N 1.67(3) C(6)-C(7) 1.60(4) C(l)-C(2)-C(3) 113.(3) C(4)-N 1.52(4) S***C(4) 2.64(3) C(2)-C(3)-C(4) 113.(3) S-C(l) 1.82(3) 1(1)-1(2)-I(3) 178.6(l) C(3)-C(4)-N 110.(2) S-C(7) 1.77(3) C(4)-N-S 112(2) C(5)-C(4)-N 113(2) C(l)-C(2) 1.55(4) N-S-C(l) 100 (1) C(3)-C(4)-C(5) 117.(3) C(2)-C(3) 1.59(4) N-S-C(7) 108(l) C(4)-C(5)-C(6) 114.(2) C(3)-C(4) 1.50(4) C(l)-S-C(7) 105(l) C(5)-C(6)-C(7) 112.(3)