The application of formyl group activation of bromopyrrole esters to formal syntheses of lycogarubin C, permethyl storniamide A and lamellarin G trimethyl ether

Gupton, John T.; Telang, Nakul; Patteson, Jon B.; Lescalleet, Kristin; Yeudall, Scott; Sobieski, John; Harrison, Andrew; Curry, Will

doi:10.1016/j.tet.2014.11.035

Cited by 9 publications

(3 citation statements)

References 26 publications

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“…More than fifty lamellarins have been isolated, mainly from marine sponges, since the first isolation of lamellarins A–D was reported by Faulkner and Clardy (Figure ). The lamellarins possess various biological activities and are structurally complex, compared with the related natural products, ningalins, lukianols, didemnimides, dictyodendrins, polycitrins, and storniamides . Tremendous synthetic efforts have been made toward the total synthesis of lamellarins by Fürstner, Steglich, Banwell, Iwao/Ishibashi, Boger, Gupton, ,, Ruchirawat, Álvarez, Handy, Opatz, Jia, Itami/Yamaguchi, Yang, Wu/Wu, Chandrasekhar, and Michael groups.…”

Section: Introductionmentioning

confidence: 99%

Total Synthesis of Lamellarins G, J, L, and Z Using One-Pot Halogen Dance/Negishi Coupling

et al. 2021

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A bottom-up synthesis of lamellarins G, J, L, and Z was achieved via one-pot halogen dance/Negishi coupling of a lithiated dibromopyrrole derivative. The easily accessible dibromopyrrole bearing an ester moiety underwent halogen dance smoothly at −78 °C within 10 min. The resultant α-pyrrolyllithium was transmetalated to the corresponding organozinc species, which was then coupled with an aryl iodide in the presence of catalytic palladium to provide the fully substituted pyrrole. Subsequent halogen–lithium exchange was performed to incorporate a boronate group exclusively at the β position proximal to the ester moiety. This synthetic intermediate allowed stepwise diarylation for the total synthesis of lamellarins G, J, L, and Z.

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Section: Introductionmentioning

confidence: 99%

Total Synthesis of Lamellarins G, J, L, and Z Using One-Pot Halogen Dance/Negishi Coupling

et al. 2021

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“…These synthetic strategies can be classified into two categories, namely, pyrrole construction from acyclic precursors 4 5 6b d , 7` b c , 8 9a 10 11a 13 14 , 16 17 18 19 20 and stepwise functionalization of the pivotal pyrrole skeleton. 6a c 7d e 9b c 11b c 12 15 Recently, our research groups achieved the total synthesis of lamellarins and their congeners using the latter method. 21 Herein, we report the total synthesis of structurally similar lamellarins U 6d 7e 10c 11a 13a 19a 22 and A3 6d 23 24 through development of a stereoselective functionalization of a multiply halogenated pyrrole.…”

Section: Table 1 Screening Of Reaction Conditions To Su...mentioning

confidence: 99%

Total Synthesis of Lamellarins U and A3 by Interrupting Halogen Dance

et al. 2022

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A total synthesis of lamellarins U and A3 is described. The synthesis features interruption of a halogen dance reaction of a metalated α,β-dibromopyrrole. The pyrrolylmagnesium reagent, generated by deprotonative metalation using (TMP)MgCl·LiCl (TMP: 2,2,6,6-tetramethylpiperidide) as base, was transmetalated to the corresponding organozinc species without causing the halogen dance reaction, which underwent a Negishi coupling to incorporate an aryl group onto the pyrrole ring. The arylated α,β-dibromopyrrole was then converted into lamellarins U and A3 through an α-selective halogen–magnesium exchange followed by carboxylation and subsequent palladium-mediated cyclization. The late-stage introduction of another aryl group was performed using a Kosugi–Migita–Stille coupling to provide lamellarins U and A3.

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“…Hence, the common intermediate 158 was prepared by the sequential route in 27% over five steps (starting from already prefunctionalized 2,3,5-trisubstituted pyrrole 168 ) or by the convergent route in 16% over eight steps (starting from desoxyveratroin 171 , Scheme 27 ). Gupton also developed approaches to functionalized pyrroles suitable as precursors to type-I and type-II lamellarins and most recently published a second formal total synthesis of lamellarin G trimethyl ether [ 95 , 96 ].…”

Section: Synthesis Of Type-i Lamellarins—miscellaneous Approachesmentioning

confidence: 99%