A Stereospecific '2-Aza-divinylcyclopropane' Rearrangement

Article Article scientifique Article A Stereospecific '2-Aza-divinylcyclopropane' Rearrangement eng 2000 author Muller Paul 24995 author Toujas-Bernate Jean-Louis 514088 author Bernardinelli Gérald Hugues 24765 1525-1534 10.1002/1522-2675(20000705)83:7<1525::AID-HLCA1525>3.0.CO;2-1 0018-019X http://doi.wiley.com/10.1002/1522-2675%2820000705%2983%3A7%3C1525%3A%3AAID-HLCA1525%3E3.0.CO%3B2-1 The stereochemical course of the thermal 2‐aza‐Cope rearrangement of the optically pure acyl azide (−)‐(1S)‐5 was investigated by determination of the absolute configuration of the rearrangement product (1R,8S)‐9. The reaction proceeds by a sequence of stereospecific steps from 5 to an equilibrating mixture of exo‐ and endo‐isocyanates 6 and 7. The endo‐isomer 7 undergoes Cope rearrangement to the putative intermediate 8, which is trapped and characterized as the adduct 9b of butan‐1‐ol. The absolute configuration of 9b was determined by its reduction to the amide 20, and determination of the X‐ray structure of the N‐camphanoylamide 21 derived from camphanic acid of known absolute configuration. Dewey 540 36 Département de chimie organique 141 false Helvetica Chimica Acta 83 7 ca9fe8e4-054f-4db1-ac0f-d1e7892714b2 Article (Published version) Restricted M-ller_et_al-2000-Helvetica_Chimica_Acta-1.pdf 212446 application/pdf restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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A Stereospecific '2-Aza-divinylcyclopropane' Rearrangement	Helvetica Chimica Acta			2000	362	0

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Toujas-Bernate, Jean-Louis