23185-51-5Relevant academic research and scientific papers
THE KETENE THIOACETAL GROUP AS A CATIONIC CYCLIZATION TERMINATOR. A SYNTHESIS OF THE PYRROLIZIDINE RING SYSTEM.
Chamberlin, Richard A.,Chung, John Y. L.
, p. 2619 - 2622 (1982)
A cationic cyclization to the pyrrolizidine ring system is reported in which a ketene thioacetal group serves as an efficient terminator for 5-membered ring formation. (+/-)-Supinidine is prepared using this methodology.
Transalpinecine and Analogues: First Total Synthesis, Stereochemical Revision and Biological Evaluation
Dehoux, Cécile,Castellan, Tessa,Enel, Morgane,André-Barrès, Christiane,Mirval, Sandra,Becq, Frédéric,Ballereau, Stéphanie,Génisson, Yves
, p. 1830 - 1834 (2019)
The first total synthesis of transalpinecine, a pyrrolizidine alkaloid extracted from Heliotropium transalpinum is reported. The concise synthetic route developed towards these unusual iminosugar-like natural compounds relies on an intramolecular Morita–Baylis–Hillman reaction. The four diastereoisomers of transalpinecine, as well as the two diastereoisomers of the parent epoxide subulacine, were prepared. 1H NMR-based stereochemical assignment of these different diastereoisomers was substantiated by quantum calculations of NMR shifts and coupling constants, allowing revision of the initially reported transalpinecine structure. One of these synthetic compounds significantly potentiates the activity of the F508del-CFTR corrector VX-809.
Cationic Cyclizations of Ketene Dithioacetals: A General Synthesis of Pyrrolizidine, Indolizidine, and Quinolizidine Alkaloid Ring Systems
Chamberlin, A.Richard,Nguyen, Hoa D.,Chung, John Y.L.
, p. 1682 - 1688 (1984)
Cyclizations of ketene dithioacetals have been applied to the synthesis of pyrrolizidine, indolizidine, and quinolizidine alkaloid ring systems.This new cationic cyclization terminator allows the efficient formation of 5-, 6-, and 7-membered heterocyclic rings, as illustrated by the preparation of 10a-e.Several of these products, available in three steps, have been converted into the known alkaloids (+/-)-supinidine, (+/-)--trachelanthamidine, (+/-)-elaeokanine A, and (+/-)-epi-lupinine.
Expedient pyrrolizidine synthesis by propargylsilane addition to N-acyliminium ions followed by gold-catalyzed α-allenyl amide cyclization
Breman, Arjen C.,Dijkink, Jan,Van Maarseveen, Jan H.,Kinderman, Sape S.,Hiemstra, Henk
supporting information; experimental part, p. 6327 - 6330 (2009/12/24)
(Chemical Equation Presented) A reaction sequence, involving the addition of (substituted) propargylsilanes to lactam-derived N-acyliminium ions followed by gold-catalyzed cyclization of the resulting α-allenyl amide, is applied in expedient syntheses of
Synthesis of the necine bases (±)-macronecine and (±)-supinidine via an aza-ene reaction and allylsilane induced ring closure
Sarkar, Tarun K.,Hazra, Anindya,Gangopadhyay, Pulak,Panda, Niranjan,Slanina, Zdenek,Lin, Chun-Cheng,Chen, Hui-Ting
, p. 1155 - 1165 (2007/10/03)
An aza-ene reaction has been used for the first time for the synthesis of two 5-membered lactam-hydrazides, each with a built-in allylsilane terminator for further elaboration. One of the lactam-hydrazides was transformed via an allylsilane-hydrazonium io
A synthesis of (±)-Supinidine via an intramolecular carbenoid-thioimide coupling reaction
Kim, Guncheol,Kang, Sunwha,Keum, Gyochang
, p. 3747 - 3748 (2007/10/02)
Intramolecular diazoketoester-thioimide annulation reaction in the presence of rhodium(II) acetate dimer provided a new way to pyrrolizidine skeletons (±)-Supinidine was synthesized by subsequent manipulations.
Intramolecular Allylstannane Cyclizations in Alkaloid Synthesis: Applications to Pyrrolizidine Alkaloids
Keck, Gary E.,Cressman, Erik N. K.,Enholm, Eric J.
, p. 4345 - 4349 (2007/10/02)
Syntheses of (+/-)-isoretronecanol, (+/-)-supinidine, (-)-dihydroxyheliotridane, and (+)-heliotridine are detailed.The key step in each case involves an intramolecular acyliminium ion cyclization onto a suitably positioned allylstannane for construction o
MILD METHODOLOGY FOR PYRROLINE ANNULATION. SECOND GENERATION SYNTHESIS OF PYRROLIZIDINE ALKALOIDS.
Hudlicky, Tomas,Sinai-Zingde, Gurudas,Seoane, Gustavo
, p. 1155 - 1164 (2007/10/02)
Vinylaziridine 2 underwent alkylative ring opening with trimethylsilyl iodide to furnish supinidine ethyl esters 4 from which supinidine 5, isoretronecanol 7, and trachelanthamidine 9 were synthesized stereoselectively.
Pyrrolizidinone and Indolizidinone Synthesis: Generation and Intramolecular Addition of α-Acylamino Radicals to Olefins and Allenes
Burnett, Duane A.,Choi, Joong-Kwon,Hart, David J.,Tsai, Yeun-Min
, p. 8201 - 8209 (2007/10/02)
α-Acylamino radicals can be generated by treatment of phenylthio, methylthio, or phenylselenyl lactams of type 7, 8, and 17 with tri-n-butyltin hydride in the presence of AIBN.The radicals add intramolecularly to olefins and allenes to give indolizidinones and pyrrolizidinones.The product distribution depends on the substitution patterns of the unsaturated moiety and the legnth of the chain connecting the radical and olefinic centers.Product ratios appear to reflect the kinetic partitioning of the radical between cyclization pathways.These reactions are potentially useful in the area of pyrrolizidine alkaloid synthesis.The conversion of cyclization produts 50 and 51 to (+/-)-supinidine (1) serves as an example.
Pyrrolizidine Alkaloid Synthesis. (+/-)-Supinidine
Macdonald, Timothy L.,Narayanan, B. A.
, p. 1129 - 1131 (2007/10/02)
Synthesis of the Δ1,2-unsaturated pyrrolizidine alkaloid supinidine proceeding via regioselective N1-C2 vicinal annulation of a 1,3-dihaloalkane onto a 3-(hydroxymethyl)-3-pyrroline system is described.
