Enantioselective Syntheses of Pachastrissamine and Jaspine AviaHydroxylactonization of a Chiral Epoxy Ester

Practical Synthesis of Pachastrissamine (Jaspine B), 2-<i>epi</i>-Pachastrissamine, and the 2-<i>epi</i>-Pyrrolidine Analogue

“…47) Triol 9 would be derived from 3,4-syn-homoallylic alcohol 11. The synthesis of 11 would be accomplished via the stereoselective introduction of an allyl group into aldehyde 13, which is readily prepared from commercially available diethyl D-tartrate (14) according to the literature. 48) In addition, 2-epimer 2 would be synthesized from 3,4-anti-isomer 12 using a procedure similar to that for the synthesis of 1.…”

“…9,10) Because of its novel structural features and impressive biological activity, many total syntheses of 1 have been accomplished. [3][4][5][6][7][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] The stereoisomers of 1 have also been synthesized, 5,6,[20][21][22][23][24][25][26][27][28][29][31][32][33][34][35][36][37][38][39][40] and their biological activity investigated. Interestingly, the 2-epimer 2 6,…”

“…30) However, this route is not suitable for scalable synthesis because of the low yield of the dirhodium(II)-catalyzed C-H amination reaction. Herein, we report the practical syntheses of pachastrissamine (1), 2-epi-pachastrissamine (2), and the 2-epimer of the pyrrolidine analogue (4) from commercially available diethyl D-tartrate (14).…”

Aminohydroxylation of divinylcarbinol and its application to the synthesis of bicyclic hydroxypyrrolidine and aminotetrahydrofuran building blocks

“…In anti-cancer assays, this novel sphingosine derivative proved to be the most potent compound against the A549 human lung carcinoma cell line isolated from the Jaspis genus. The combination of potent biological properties and relatively straightforward molecular structures has led to the development of a number of its synthetic preparations (Llaveria et al, 2011;Passiniemi & Koskinen, 2011;Yoshimitsu et al, 2011;Srinivas Rao & Venkateswara Rao, 2011;Urano et al, 2010;Salma et al, 2010;Inuki et al, 2009Inuki et al, , 2010Yoshimitsu et al, 2010;Vichare & Chattopadhyay, 2010;Canals et al, 2009;Enders et al, 2008;Abraham et al, 2008, and the articles cited in their review). The biological activities of numerous synthetic analogues and epimers have also been prepared and tested.…”

Enantioselective Synthesis of Jaspine B (Pachastrissamine) and Its C‐2 and/or C‐3 Epimers

“…A few enantioselective catalytic procedures have been reported that are based on: (i) Sharpless asymmetric epoxidation of 4-benzyloxy-(2E)-butene-1-ol (Scheme 1a), [22] (ii) Sharpless asymmetric dihydroxylation of ethyl (2E)-heptadecenoate (Scheme 1b), [23] and (iii) methyl (2E)-5-p-methoxybenzyloxy-2-pentanoate (Scheme 1c). [24] Recently, an asymmetric organocatalytic method that uses a proline-catalyzed aldol [25] or oxidation [26] reaction as a key step and a diastereoselective synthesis based on the tandem conjugate addition of a chiral lithium amide to a triisopropylsilyloxy-α,β-unsaturated methyl ester followed by enolate oxidation have been described (Scheme 1d). [27] …”