title: Synthesis of Pyrrolo[2,3-d]pyrimidines by Copper-Mediated Carbomagnesiations of N-Sulfonyl Ynamides and Application to the Preparation of Rigidin A and a 7-Azaserotonin Derivative.
abstract: The treatment of readily available N-alkynyl-5-iodo-6-sulfamido-pyrimidines with iPrMgCl⋅LiCl followed by a transmetalation with CuCN⋅2 LiCl produces, after intramolecular carbocupration, metalated pyrrolo[2,3-d]pyrimidines. Quenching of these pyrimidines with allylic halides or acid chlorides results in polyfunctional pyrrolo[2,3-d]pyrimidines. Further reaction with ICl and a Negishi cross-coupling, using PEPPSI-iPr as the catalyst, furnishes fully substituted N-heterocycles. A formal synthesis of the marine alkaloid rigidin A has been achieved as well as the preparation of a derivative of 7-azaserotonine, related to the natural hormone serotonin.
authors.affiliation: Ludwig Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.
authors.forename: Johannes
authors.initials: J
authors.lastname: Nickel
authors.affiliation: Ludwig Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.
authors.forename: Maitane
authors.initials: M
authors.lastname: Fernández
authors.affiliation: Ludwig Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377, München, Germany.
authors.forename: Lydia
authors.initials: L
authors.lastname: Klier
authors.affiliation: Ludwig Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377, München, Germany. paul.knochel@cup.uni-muenchen.de.
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D011758:Pyrroles / Q000138:chemical synthesis* / Q000737:chemistry; D012701:Serotonin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: C523473:7-azaserotonin; D000470:Alkaloids; D001688:Biological Products; D011725:Pyridines; D011758:Pyrroles; D012701:Serotonin; D003300:Copper; C486292:pyrrolo(2, 3-b)pyridine
keywords: N-heterocycles; azaserotonin; carbomagnesation; cyclisation; rigidin A