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. Author manuscript; available in PMC: 2018 Feb 1.
Published in final edited form as: Angew Chem Int Ed Engl. 2017 Jan 3;56(6):1624–1628. doi: 10.1002/anie.201611078

Scheme 1.

Scheme 1

Gram-scale total synthesis of (+)-mikanokryptin (1). Reagents and conditions: a) carvone (1 equiv), Na2CO3 (3 equiv), SO2Cl2 (1.2 equiv) added slowly over 2 h, DCM, 0 °C, then add CeCl3·7H2O (1.1 equiv), NaBH4 (3 equiv), MeOH, 0 °C, 1 h, 78%; b) TBDPSCl (1.2 equiv), imidazole (3 equiv), DMAP (0.05 equiv), DMF, rt, 8 h, 90%; c) O3, pyridine (0.3 equiv), DCM, −78 °C, 20–40 min, then add DMS (2 equiv), rt, 8 h, then add piperidine (0.15 equiv), AcOH (0.2 equiv), 40 °C, 16 h, 42%; d) In (1.5 equiv), 7 (1.2 equiv), 8 (1 equiv), H2O (1 equiv), DMF, rt, 8 h, 67%, 2:1 dr; e) TESOTf (4 equiv), 2,4,6-collidine (6 equiv), DCM, 0 °C, 24 h, 78%; f) SnCl2 (4.5 equiv), NaI (9 equiv), DMF, 60 °C, 12 h, 90%; g) NaOMe (0.1 equiv), MeOH, 16 h, then add AcOH (0.1 equiv), PtO2 (0.1 equiv), H2 (1 atm), 6 h, 96%; h) Rh(PPh3)3Cl (0.1 equiv), H2 (1 atm), PhH, 1 h, 54%; i) TBAF (3 equiv), THF, rt, 24 h; DBU (1.1 equiv), toluene, DCM, Δ, 69%; j) MnO2, DCM, rt, 16 h, 97%; DMS = dimethylsulfide, TBDPSCl = tert-butyldiphenylsilyl chloride, TESOTf = triethylsilyl trifluoromethanesulfonate, TBAF = tetra-n-butylammonium fluoride, DBU = 1,8-Diazabicyclo[5.4.0]undec-7-ene. All X-ray structures shown were obtained during preliminary studies conducted with (−)-carvone.