Synthesis of (+)-Lycoricidine by the Application of Oxidative and Regioselective Ring-Opening of Aziridines

Abstract

A highly stereoselective total synthesis of (+)-lycoricidine has been described. The salient features of this synthesis are the one-pot elimination followed by allylation reaction, ring-closing metathesis, stereoselective aziridine formation, Dess-Martin periodinane, and silica gel mediated oxidative ring-opening of aziridine to form alpha,beta-unsaturated ketone (allyl amine) and intramolecular Heck cyclization.

Mechanically activated ring-opening reactions of N-acyl-1,2,3,4-tetrahydroisoquinolines derived from the synthesis of praziquantel intermediate

“…The oxidative ring opening of heterocycles, 6 metal-containing heterocycles 7 and carbocycles 8 are well documented, these valuable ring-opened synthetic intermediates can be further manipulated to afford ring-contraction or ring-expansion products. 9 In addition, a great number of works have applied oxidative ring opening reaction to the synthesis and modification of bioactive natural products, such as Lavandulol, 10 (þ)-Lycoricidine, 11 Taxane derivatives 12 and Paclitaxel analogs. 13 However, most of the oxidative ring-opening reactions are conducted in hazardous organic solvents, together with metal oxidants or other explosive oxidants.…”

Control of Olefin Geometry in Macrocyclic Ring-Closing Metathesis Using a Removable Silyl Group

“…Post-metathesis functionalization has in general been limited to ‘symmetrical’ transformations such as hydrogenation, dihydroxylation, 6d, 8 epoxidation 8b, 9 and aziridination. 10 …”

Synthesis of Amaryllidaceae Constituents and Unnatural Derivatives

“…[85] Furan 95 was obtained from d-(+ +)-mannose in asequence of reactions according to ap reviously published protocols. [85] Furan 95 was obtained from d-(+ +)-mannose in asequence of reactions according to ap reviously published protocols.…”

“…In the case of Banwells synthesis [74] of (À)-lycoricidine (4), Suzuki cross-coupling was employed to to connect ring Aand ring C. Yadav [85] synthesized (+ +)-lycoricidine (4)s tarting with d-(+ +)-mannose.H ea pplied ring closing metathesis, Yamada-Jacobsen-Evans aziridination, Heck cross-coupling, and Luche reduction in his synthesis.P anda utilized an intramolecular aldol reaction to furnish ring Cand aBanwell modified Bischler-Napieralski reaction [31] to establish ring B. In the case of Banwells synthesis [74] of (À)-lycoricidine (4), Suzuki cross-coupling was employed to to connect ring Aand ring C. Yadav [85] synthesized (+ +)-lycoricidine (4)s tarting with d-(+ +)-mannose.H ea pplied ring closing metathesis, Yamada-Jacobsen-Evans aziridination, Heck cross-coupling, and Luche reduction in his synthesis.P anda utilized an intramolecular aldol reaction to furnish ring Cand aBanwell modified Bischler-Napieralski reaction [31] to establish ring B.…”