Highly Selective Entry to the Azadirachtin Skeleton via a Claisen Rearrangement/Radical Cyclization Sequence

Organic Letters

Volumn 4, Issue 22, 2002, Pages 3847-3850

  Durand Reville, Thomas ^a   Gobbi, Luca B ^a   Gray, Brian Lawrence ^a   Ley, Steven V ^a   Scott, James S ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

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EID: 0042152201     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0201557     Document Type: Article

References (50)

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41. A fully automated Coherent Synthesis System microwave machine was used. This was supplied by Personal Chemistry: Hamnesplanaden 5, 753 19 Uppsala, Sweden; www.personalchemistry.com.
42. Stereochemistry was determined by nOe experiments and by comparison to a crystal structure obtained for an analogous compound (unpublished). See Supporting Information for full details.
43. Reliability was determined by iterative transformation of 15 different samples of 17. To date, we have never observed decomposition using these reaction conditions. Typical procedure: A 5-mL base-washed microwave vial was charged with 17 (9.50 mg, 0.012 mmol) and sealed. To the solid was added 1.0 mL of degassed 1,2-dichlorobenzene. The resultant mixture was subjected to 15 separate, 60-s microwave pulses, punctuated by 90-s cooling periods. After final cooling of the pale yellow solution, it was loaded onto a plug of silica gel and chromatographed with petroleum ether to remove the 1,2-dichlorobenzene, and subsequently EtOAc to remove the allene 6 (8.36 mg, 88%) as a white foam after solvent removal in vacuo. Attempts to scale this reaction have proceeded uneventfully.
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50. Neither the LHF nor the RHF alone have significant antifeedant activity. For previous SAR studies, see: (a) Blaney, W. M.; Simmonds, M. S. J.; Ley, S. V.; Anderson, J. C.; Toogood, P. L. Entomol. Exp. Appl. 1990, 55, 149. (b) Ley, S. V.; Santafianos, D.; Blaney, W. M.; Simmonds, M. S. J. Tetrahedron Lett. 1987, 28, 221-224.