@article{05b9e32bdfae496081ccd403e240cfec,
title = "The first total synthesis of the antitumor macrolide rhizoxin: Synthesis of the key building blocks",
abstract = "The construction in optically pure form of the key building blocks, arising from our retrosynthetic analysis of the antitumor macrolide rhizoxin is described.",
author = "Masahisa Nakada and Susumu Kobayashi and Shigeo Iwasaki and Masaji Ohno",
note = "Funding Information: References + Instituteo f AppliedM icrobiologyU, niversityo f Tokyo.Y ayoi, Bunkyo-kuT. okyo 113,J apan La) Iwasaki,S .; Kobayashi,H .; FurukawaJ,. ; Namikoshi,M .; Okuda,S .; Sato.Z .; Matsuda.1O; da,T . J. Anribior.1 9S4.37,3 54.b ) Iwasaki,S .; Namikoshi,M .; KobayashiH, .; Furukawa.J. ; Okuda,S .;Itai. A.; Kasuya,A .; Iitaka.Y .; Sato,Z . J. Antibiot.1 986.39,424c. ) Iwasaki,S .; Namikoshi,M .; Kobayashi,H .; Furukawa.J .; Okuda,S . Chem.P harm.B ull. 1986.34.1 384.d ) TakahashiM. .; Iwasaki.S .; Koba ashi,H .; Okuda,S .; Murai, T.; Sato.Y .; Haraguchi-HiraokaT.,; Nagano,H . J. Anribiot.1 987.4d , 66. e) Kobayashi.H .; Iwasaki,S .; Yamada,E .; Okuda,S . J. C/rem.S ot., Chem.Commun1. 986, 1702. 2.a)T akahashiM, .; Iwasaki,S .; KobayashiH. .; Okuda,S .; Murai, T.; Sato,Y . Biochem. Biophys. Aczu 1987.926.215. b) Sullivan,A . S.; Plasad,V .; Roach,M . C.; TakahashiM, .; Iwasaki.S .; LuduenaR, . F. Cuncer Res. 1990,50,4277. c) Kato, Y.; Ogawa.Y .; Imada,T .; Iwasaki,S .; ShimazakiN, .; Kobayashi,T .; Komai. T. J. Anribior. 1991.44, 66. ~.TSUNO. T.; Oh-ham.T .; Iida, H.; TsukagoshiS. .; Sato,Z .; MatsudaS, .; Iwasaki,S .; Okuda,S .; Shin&u, F.; SasagawaK, .; Fukami,M .; Fukuda,K .; Arakawa,M . CancerR es. 1986,46,381. 4.NakadaM, .; Kobayashi,S .; Ohno,M .; lwasaki.S .; Okuda.S . Tetrahedron Lerr. 1988, 3951. 5.a) Brown, H. C.; Negishi,E .; Terrahedron 1977,33.2331. b) Chan,K . -K.; Saucy,G . J. Org. Chem. 1977,42,3828. c) Still, W. C.; Darst,K . P. J. Am. Chem.S ot. 1977,42,3 828.d ) Still, W. C.; Shaw,K . R. Terrahedron Lerr. 1981, 3725. 6.Still. W. C.; Gennari.C . Tetrahedron Lerr. 1983.4405. 7.The majord iastereomewra sc onfirmedto be4 a by 4OOMHzt H NMR afterc onversionto 9. 8.a) Corey,E . J.; Beams,D . J. J. Am. Chem.S ot. 1973,95,5 82.b ) Corey,E . J.; Kozikowski. A. P. Tetrahedron L&r. 1975,925. 9.a)B lanchetteM, . A.; Choy, W.; Davis,J . T.; EssenfeldA, . P.; MasamuneS, .; Roush,W . R.; Sakai.T . Terrahedron Lerr. 1984, 2183. lO.NakataT, .; Oishi, T. Terruhedron Lerr.1980. 1641. ll.The stereochemistorfy t hed iol wasc onfirmeda ss ynb y 400M Hz lH-NMR afterconversiontothe acetonide(J c16_1=7 11.8H z). 12.The opticalp urityw asc onfirmeda s> 98%ebey 400M Hz tH-NMR usingE u(hfc)j. 13.MancusoA. . J.; Huang, S. -L.; Swern.D . J. Org. Chem. 1978.43. 2480. 14.MasamuneS.. ; Ellingboe, J. W.; Choy, W. J. Am. Chem. Sot. 1982,104, 5526. H.Parikh, J. R.; von E. Doering,W . J. Am. Chem.S ot. 1967,89.5 505. 16.Form echanisticco nsiderationist ,w ass peculatetdh att her eductionw ouldl eadt o 3n. andt hisr esulti s alsow ell explainedb y theF elkin-Anhm odel.s ee;C herestM, .; Felkin,H .; PrudentN, . TarruhedronL en. 1968.2199.; Anh. N. T.; Eisenstein0. . Nouv.J . Chim. 1977,1,6 1.; seea lso; Midland, M. M.; Kwon, Y. C. 1. Am. Chem. Sot. 1983.105, 3725. 17.Prcpa1tdf romt hec orrespondinbgr omide{\textquoteright}*w ithr -butyllithium(2 eq.)in pentane-Et@THF(3:4:6a)t -1aX. HXorey, E. J.; Bock, M. G.; Kozikowski,A . P.; RamaR ao,A . V. Terruhedron lerr. 1978, 1051. 19.EvansD. . A.; ChapmanK, . T.; Carreira,E , M. J. Am. Chem. Sot. 1988,110, 3560. 20.NakadaM. .; Kobayashi,S .; ShibasakiM, .; Iwasaki,S .; Ohno,M . followingp aperin thisi ssue. 21.All newc ompoundesx hibiteds atisfactorayn alyticadl ata. Yieldsr efert o spectroscopicaallny d chmmatographicahlloym ogenoums aterials. 22.Thisw orkw ass upportebdy a Grant-in-Aidf or CancerR esearch(N o.61015019in). partb y a Grant-in-Aid for ScientificR esearchon PriorityA reas( No.6261600f5r)o mt heM inistryo f EducationS, ciencea nd Cultureo f Japan,a ndC IBA-GEIGY FOUNDATION (JAPAN) for theP romotiono f Science. We am indebtedto KANEKA CORPORATION for supplyingu s with( S)-methyl3-hydmxy-2-methylpropionate usedi n thee arys tages.",
year = "1993",
month = feb,
day = "5",
doi = "10.1016/S0040-4039(00)77485-5",
language = "English",
volume = "34",
pages = "1035--1038",
journal = "Tetrahedron Letters",
issn = "0040-4039",
publisher = "Elsevier Limited",
number = "6",
}