Fe(III)-catalyzed radical cyclization of cyclopropanone thioacetal

Heterocycles

Volumn 52, Issue 2, 2000, Pages 505-510

  Ohara, Hiroyuki ^c   Kudo, Kazutoshi ^a   Itoh, Toshiyuki ^a   Nakamura, Masaharu ^b   Nakamura, Eiichi ^b  

^a OKAYAMA UNIVERSITY   (Japan)

^b UNIVERSITY OF TOKYO   (Japan)

^c NONE

Author keywords

[No Author keywords available]

Indexed keywords

ACETAL DERIVATIVE; ACETONITRILE; ALKENE; CYCLOPROPANE DERIVATIVE; FERRIC ION;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; ELECTRON TRANSPORT; OXIDATION; REACTION ANALYSIS; REDUCTION;

EID: 0034143363     PISSN: 03855414     EISSN: None     Source Type: Journal    
DOI: 10.3987/com-99-s48     Document Type: Article

References (24)

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14. A preliminary account for the reaction of cyclopropanonetrimethylenethioacetal see. M. Nakamura, M. Toganoh, H. Ohara, and E. Nakamura, Organic Lett. 1999, in press.
15. Reaction of lithio 1,3-dithiane with epichlorohydrin and subsequent treatment with sodium fluoride in tetrahydrofurane (THF) afforded glycidyl 1,3-dithiane (4), and further reaction with n-BuLi gave 2-hydroxymethyl-1,1-trimethylenedithiocyclopropane (5) in more than 85% yield. This alcohol was then treated with allyl bromide or allyl chloride in the presence of sodium hydride as base and provided the desired allyl ether (1) in good overall yield (Scheme 1). (matrix presented) Scheme 1. Simple synthesis of cyclopropane dithioacetal derivatives (1)
16. 2: C, 55.51; H, 7.49. Found: C, 56.18; H, 7.60.
17. 2: C, 51.69; H, 6.94. Found: C, 51.85; H, 6.87.
18. 3CN was found to be the best.
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22. 2).
23. MacSpartan Plus was employed for MO (PM3) calculation. Calculation results (heat of formation): A: 189.98 Kcal/mol, B: 206.81 Kcal/mol, C: 188.32 Kcal/mol, D: 141.9 Kcal/mol.
24. MO (PM3) calculation results (heat of formation): cis-trans-2b: -40.78 Kcal/mol. cis-cis-2b: -38.80 Kcal/mol. The ratio of cis-trans-2b and cis-cis-2b was estimated by the difference in the heat of formation energy of these two isomers to be 96.5:3.5; this well agreed with the experimental result obtained (94:6). MO calculation suggests that cis-trans-2d, and cis-trans-2e are stable than the corresponding cis-cis isomers.