Syntheses of the racemic jaborandi alkaloids pilocarpine, isopilocarpine and pilosinine

Tetrahedron Letters

Volumn 50, Issue 26, 2009, Pages 3509-3512

  Davies, Stephen G ^a   Roberts, Paul M ^a   Stephenson, Peter T ^a   Thomson, James E ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKALOID; CHLORIDE; DIOXANE DERIVATIVE; GAMMA BUTYROLACTONE; ISOPILOCARPINE; LACTONE DERIVATIVE; NITRATE; PALLADIUM; PILOCARPINE; PILOSININE; UNCLASSIFIED DRUG;

ARTICLE; CARBONYLATION; CATALYSIS; CHEMICAL REACTION; CRYSTALLIZATION; DECARBOXYLATION; DRUG SYNTHESIS; EPIMER; HYDROGENATION; PILOCARPUS; STEREOCHEMISTRY;

PILOCARPUS JABORANDI;

EID: 65549086736     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.03.021     Document Type: Article

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57. Treatment of 9 under these conditions resulted in a change of colour of the solution from deep red to yellow, followed by the formation of a light brown precipitate.
58. The formation of (E)-α-ethylidene lactone 5 presumably arises from the isomerisation of the initially formed α-vinyl lactone 8, under the influence of the basic imidazole ring.
59. Since hydrogenation of exclusively (E)-5 gave a 72:28 mixture of pilocarpine 1 and isopilocarpine 2 in quantitative yield, and hydrogenation of an 88:12 mixture of (E)- and (Z)-α-ethylidene lactones 5 (obtained from our first generation synthesis) produced a 70:30 mixture of pilocarpine 1 and isopilocarpine 2 in quantitative yield, this indicates that the double bond geometry within 5 does not have a major impact on the product distributions obtained.
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61. An authentic sample of (+)-pilocarpine 1 was kindly supplied by Macfarlan Smith Ltd, Edinburgh; base-catalysed epimerisation of this sample also provided a diastereoisomerically pure sample of (+)-isopilocarpine 2.