有机化学习题福山组会题2005年104

15234COCl 1) SnCl 4, CH 2Cl 2;DBU, 67%2) LDA, THF;TMSCl, 75%SnCl 4methyl vinyl ketoneCH 2Cl 261%J. Clardy et al ., J. Am. Chem. Soc., 116, 8378 (1994)1) CH 3CO 3H(> 2 eq)AcONaAcOH, 70°C 2) KOH, MeOH; HCl (pH < 1)3) TBDPSCl, imidazole DMF, 33%(3 steps)O OTBDPSOOMeMeOOHCHO1) di-tert -butyl malonate piperidine, AcOH benzene, reflux, 91%2) 3-methyl-1-butene h ν, benzene, 88%3) Me 3S +(O)·I -, NaH DMF, rt, 94%4) p -TsOH, toluene reflux, 55%MeOMeOO H HOi -Pr S. Ohta et al ., Heterocycles , 65, 1099 (2005)OOMeO OMeMeOOMe1) DIBAL, toluene 2) (MeO)2P(O)CHN 2 t -BuOK, THF 70% (2 steps)3) MsCl, 2,6-lutidine 50 °C4) CaCO 3, wet MeOH 50 °C 72% (2 steps)MeOOMeCO 2MeV. H. Rawal et al ., J. Am. Chem. Soc., 125, 13022 (2003)HN OHBr N MeN O OSePh 1) Bu 3P, THF, 0 °C 81%2) xs. NaNH 2, liq. NH 3 86%C 16H 21NSeBu 3SnH cat. AIBN PhH reflux 40%Shipman, M. et al ., Tetrahedron 58, 7165 (2002)C 10H 18BrNOAllocN HCO 2MePh I 2, MeCN-H 2O 60 ˚C 92%H 2NCO 2MePhR. H.Szumigala et al, Tetrahedron Lett ., 46, 4403(2005)15234A. G. Martinez et al ., Tetrahedron Lett , 46, 5157 (2005)OH1) O 3, CH 2Cl 2, –78 °C 2) Me 2S 74% (ca. 4/1)OH+OCO 2HO OPh MePh PhMeMeH OOMePhMePhMeTiCl 4 (3 eq)CDCl 3rt 93%T. Oshima et al ., J. Org. Chem., 69, 4577 (2004)R. P. Hsung et al ., J . Am . Chem . Soc ., 125, 12694 (2003)NBnO 2Ct -BuOKTHF 46%DMDO CH 2Cl 2, –45 °C75%OO ONBnO 2C single diastereomerH MeO MeONHTsSnBu 3OTIPSMeO MeONO1) PhI(CN)OTf CH 2Cl 2 –40 °C 2) LHMDS DME –40 °CKF Al 2O 3K. S. Feldman et al., J. Am. Chem. Soc., 124, 11600 (2002)N O H H CHOPhONNH H CHOOPhONH H OPhOO Me HMeNHOH toluene rt to reflux1) MeNHOH benzene reflux 2) H 3O + CHCl 3NOH H CHOPhOB. Alcaide et al ., Tetrahedron Lett., 41, 1647 (2000)OFukuyama Group - Group Meeting Problems107/27/20055Solution:Uchida234C. H. Heathcock et al ., J. Org. Chem., 60, 1120 (1995)HO Phas above150 °C 35%O Ph R. L. Danheiser et al ., J. Am. Chem. Soc. 120, 9378 (1998)O Phγ-terpinene (radical inhibitor)toluene, 180 °C (sealed tube)70%O PhK. Harano et al., Tetrahedron , 52, 13909 (1996)O SS SHHo -dichlorobenzenereflux 46%(cis /trans = 65/35)OHTBSO1) NaHphenyl vinyl sulfoxide THF rt, 3 h 100%2) NaHCO 3 Ph 2O260 ºC, 25 min3) TBAF THF rt, 2.5 h60% (2 steps)4) PCC CH 2Cl 2 79%OO K. Ogasawara et al ., Synlett 319 (1996)T. Mandai et al ., Tetrahedron Lett . 4041 (1990)HNONHO1) DIBAL, toluene, reflux 2) PhNCO, CH 2Cl 2, rt 3) HCO 2H, 100 °C 4) KOH, MeOH, refluxErick Cuevas-Yanez et al ., Tetrahedron., 60, 1505 (2004)1) BrCH 2CO 2Et, Zn, THF, reflux, 8h 2) TsN 3, Et 3N, CH 2Cl 2, rt, 12h 3) Rh 2(OAc)4, ClCH 2CH 2Cl, reflux, 3hN CH 3CH 2CN N CH 3OCO 2Et。

54123OOH CO 2EtFEtO 2CR 2NN Cl ClClClO ONR 2 =NH NH 2O HPPh 3 (2.5 eq.)CCl 4 (3.0 eq.)DBU (3.0 eq.)MeCN A(COCl)2, DMF (cat.)DCE, 40 min;evaporation;A , DCE, 2 h; H 2O, overnightZnBr 2 (cat.)i-Pr 2NH CH 2Cl 235 minOCO 2EtFEtO 2CR 2N N 2M. M. Bio, et al ., Synthesis , 19 (2005)A. Papagni et al ., Eur. J. Org. Chem., 1149 (2001)3) MsCl, Et 3N, 0 °C4) NaOH, EtOH 70% (3 steps)Cr(CO)61) MeLi, Et 2O; MeI;pyrrolidine, Et 2O 86%2) n -BuLi, –78 °C;MeCHO, –78 °CCHOC 6H 44-NO 21) LDA, THF –78 °C; 74%IncludingCrBurgess rgt. (3 eq.)THF 25%ONH 4-NO 2C 6H 4MeO 2CCO 2MeMeMeMeO BrMgMeMe (2 eq)(Cp)2TiCl 2THF –40 °C to rt51%CHOOBn LDA THF –78 °C 81%1) Ac 2OEt 3N, DMAP CH 2Cl 2 rt2) NaCN DMSO 130 °C51% (2 steps)[Rh(CO)2Cl]2 (0.5 mol%)toluene 110 °C 93%MeHMeMe OBnC 25H 36OP. A. Wender et al ., Org. Lett., 2, 2323 (2000)OCHO CO 2Et1) SmI 2MeOH-THF 2) TBSCl, Im DMF1) LiOH, MeOH 2) i -BuO 2CCl Et 3N, Et 2O; CH 2N 23) Cu(CF 3COCHCOCF 3)2 (5 mol%)CH 2Cl 2, refluxO H HOOTBSthree stereocentersJ. S. Clark et al ., Angew. Chem. Int. Ed., 46, 437 (2007)OTIPSORMe 1) LDA, HMPA THF, −78 °C; TMSCl, to 0 °C; HCl, H 2O, 74%2) s -BuLi, PPh 3CH 3Br THF, −78 °C to 0 °C 85%1) TBAF, THF quant2) Red-Al, Et 2O 0 °C; −78 °CNIS, 97%1) TBSCl, imidazole DMF, 97%2) PPh 3, Ag 2CO 3 Pd(OAc)2, 65 °C; TBAF, THF 90 %MeHOHRL. E. Overman et al ., J. Am. Chem. Soc., 121, 5467 (1999)R = (CH 2)3CH(OCH 2CH 2O)54123X P =1) NH 2OH·HCl NaOH EtOH-H 2O 2) Cl 2, CH 2Cl 2 78% (2 steps)NaHMDS THF, –78 °C;A ;1N HCl aq.64%1) NaBH 3CN, MeOH 2) NaH, toluene, reflux; n -BuLi, CeCl 3 –78 o C to rt 59% (2 steps)W. Oppolzer et al ., Tetrahedron Lett., 35, 7015 (1994)OA(C 6H 10ClNO)X POn -C 7H 15OON Hn -C 7H 15n -BuN SO 2OMeMeO MeONOMeMeO MeONO 1) KCN (6.0 eq) Boc 2O (3.0 eq) CH 2Cl 2-H 2O 15 h, 96%2) DIBAL toluene –78 °C, 3 h 63%TosMIC (1.0 eq)K 2CO 3 (1.0 eq)MeOH reflux, 1 h;KOH, reflux, 6 h82%C 14H 13NO 3tricyclic compoundC 22H 24N 2O 6o -dichlorobenzenereflux, 20 h90%J. K. Cha et al., J. Am. Chem. Soc ., 123, 3243 (2001)NO OMeO 2CSEtO Ac 2O, TsOH toluene 70%NOOCO 2Me MeO MeOMeO MeOA. Padwa et al., J. Org. Chem., 61, 4888 (1996)PhMeO 1) DMF, POCl 3CH 2Cl 2, 0 °C to rt 2) NaN 3, DMF, rt 3) hv (Pyrex filter) MeCN, rt1) Ph 3P, toluene reflux94% (E /Z = 92/8)2) DMAD, toluene reflux, 55%NCO 2MeCO 2Me PhT. Nakata et al., Heterocycles , 48, 2551 (1998)monocyclic compoundC 9H 7NOClSMeBrO1) hexamethylenetetramine CHCl 3, rt2) conc. HCl, EtOH, rt (acidic workup)3) 2,5-dimethoxytetrahydrofuran NaOAc, AcOH, 100 °C 75% (3 steps)SN OCl4) NaIO 4 (1 eq) MeOH-H 2O, rt 89%5) TFAADMF, 0 °C 42%V. Nacci et al., J. Med. Chem., 41, 3763 (1998)54123OEt P(OEt)2O OH O Ba(OH)2 wet THF rt, 86%2) TFA Et 3SiH CH 2Cl 2 0 o C, 71%C 13H 19NO 21) Ac 2O, Et 3N, CH 2Cl 22) LHMDS, toluene, –78 to 80 o C 77% (2 steps)3) DIBAL, toluene, –78 o C, 59%1)NH 2MeO MeOTsOH (10 mol%)toluene refluxN HN. A . Magomedov et al., J. Org. Chem . 72, 3808 (2007)Me 2C NNHCO 2MeA C 6H 12N 2O 3N MeCO 2H1) DPPA, TEAPb(OAc)4MeOH 40-80%N MeNMeO MeOOJ. Warkentin, Synthesis , 279 (1970)James H. Rigby, Patrick J. Burke, Heterocycles, 67, 643 (2007)2) toluene, refluxA *toluene, reflux75%*Theoretically: 2.0 eqMeO OMeO H MeHTBSOMeOLiTMP (1.0 eq)*, TMSCl (1.0 eq)*THF, –78 to 0 ºC;Pd(OAc)2 (0.5 eq), CH 3CN68% (2 steps)6N NaOH (4.0 eq)aq. H 2O 2 (3.0 eq),MeOH, 0 ºC, 83%;Li, NH 3, THF, –33 ºC, 63%;aq. HF/CH 3CN (5:95 v/v)86%O HMeOHOMeOH* theoretical amountS. J. Danishefsky et al., Angew. Chem. Int. Ed., 46, 2199 (2007)N TrNHMeO MeOOOH1) SeO 2, TBHP, CH 2Cl 2, 90%2) NaH, AllylBr (theoretically 1 equiv) THF, 73%3) DBU, toluene, 220 °C, 75%4) TPAP, NMO (theoretically 1 equiv) MS4A, CH 2Cl 2, 70%OOL. Barriault et al., Org. Lett., 4, 1371 (2002)OTBSCONEt 22NMe CONEt 2Ph G. Bélanger et al., J. Org. Chem ., 72, 1104 (2007)1) Jones' reagent, acetone, 0 °C, 96%2) SOCl 2, CH 2Cl 2, 0 °C to rt; evaporation; PhNHCH(Me)CO 2Me, toluene, 89%3) LiOH·H 2O, THF-H 2O, reflux, 99%4) DCC, CH 2Cl 2, 89%。

15234J. D. Winkler et al., J. Am. Chem. Soc., 111, 4852 (1989)HNOn C 5H 13O CO 2t BuHNOOO n C 5H 131) acetone, TFA, TFAA, 84%2) h ν3) NaBH 4, EtOH4) NaH, THF, 60% (2 steps)L. E. Overman et al ., J. Am. Chem. Soc ., 127, 18054 (2005)L. E. Overman et al ., J. Org. Chem., 57, 1035 (1992)SEM NON1) MeOTf, CH 2Cl 22) Na 2Fe(CO)4 NMP, CO 50 °C 59% (2 steps)SEM NOMeNOA. Bhattacharjya et al ., Org. Lett., 7, 207 (2005)Mei -Pr1,3-dithiane n -BuLiTHF, –78ºCNaHBr HgCl 2CaCO 3MeCN-H 2O63%i -Pr MeMeHMe O1) isopropenyl lithium Et 2O, 0 °C 2) PBr 3Et 2O, 0 °CMeHMe MeSS3)MeCN 4) NaH, THFreflux, 6 hMeSSNaN NHTs D. A. Evans et al., Tetrahedron Lett., 47, 4691 (1973)n-Bu1) HBBr 2·SMe 2, CH 2Cl 22) , THFO 3) Bu 3SnH(0.01eq),NaBH 3CN(2.5 eq), THF 4)NN N OMe MeMe , benzene; H 2O, reflux 80 % (2steps)OHOH Bu HHR. A. Batey et al., Angew. Chem. Int. Ed., 38, 1798 (1999)15234OHOPOCl 3, DMF 75 °C;H 2O 80%C 10H 6O 31) p -anisidine p -TsOH·H 2Otol, reflux (Dean-Stark)2) CH 2=C=CHCO 2Et PPh 3 (cat)benzene, reflux, 55%ON OCO 2EtPMPP. S. Ishar et al ., Org. Lett., 2, 2023 (2000)O 3SNEtO FmocHNCO 2HNNHFmoc S Oi -Pr 2NEt MeCNCH 2Cl 2V. L. Boyd et al ., Tetrahedron Lett., 31, 3849 (1990)NCO 2Me N 2OCu(acac)2 (10 mol%)toluene, refluxNOMeO 2CF. G. West et al., Org. Lett., 7, 2949 (2005)cis : trans = 3.6 : 1Robert A. S. et al ., J. Org. Chem ., 69, 1598 (2004)1) NH 2OH.HCl NaOAc, MeOH rt, 24h 2) 190 °C(sealed tube) toluene, 3.5h 59% (2steps)ONC Tricyclic compound1) DIBAL, toluene -78 °C,2h, 100%2) n-PrP +Ph 3Br - KHMDS, THF -40 °C,24h, 62%3) H 2, 10%Pd/C MeOH, 69%NCHN HOt -BuO t -BuOTMS N C SOO OO OMs1) NH 2NH 2·H 2O neat, rt 2) TBSOTf, pyr. CH 2Cl 2, 0 °C 85 % (2 steps)3) LTA, toluene, rt 48 %OOTBSOOAcO A. Vassella et al ., Helv. Chim. Acta , 87, 2405 (2004)15234Y. Six et al ., Euro. J. Org . Chem ., 70, 4654 (2005)NO R R =MeOTi(O i -Pr)4 (1.4 eq)c C 5H 9MgCl (4.5 eq)THF, 20 ºC87%NRHOOOTBDPS O O SnCl 4CH 2Cl 2– 78 ºC 48%OO H OHHOTBDPSOL. Barriault et al., Org. Lett., 7, 5921 (2005)N OHNMe MeClPhO1)K 2CO 3, NaI 12 h, reflux 80%2) m CPBA (1.0eq) CH 2Cl 2 12 h, rt 90%3) MeOH 2 h, reflux 86%N OMeNOMePhO Me M. Abass et al ., Heterocycles , 65, 901 (2005)OEEOAc1) LAH, THF, rt 76% (2 steps)2) ClSO 3HCH 2Cl 2, –78 °C 3) H 2, Pd/C cHex, rt43% (2 steps)O +O+OHH 253045::R. L. Snowden et al., Helv. Chim. Acta , 88, 3055 (2005)OOPh Ph 1) NIS (2.5 eq) MeCN-H 2O 0 °C, 62%2) DDQMeCN-H 2O 60 °C, 58%3) NaClO 2, 2-methyl-2-butene NaH 2PO 4, t -BuOH-H 2O rt, 92%4) CAN, MeCN-H 2O, rt; K 2CO 3, rt, 80%OOIOY. Kita et al ., Angew. Chem. Int. Ed., 44, 734 (2005)。

54123R. J. Stoodley et al ., Tetrahedron Lett ., 10, 941 (1967)NSH CO 2H H 2N ONaNO 2 (3 eq)* , HClMeOHN HS MeOOOOOOMe OMe1) p -TsOH·H 2O MeNO 270 °C, 90%2) DIBAL, toluene –78 °C, 100%3) BF 3·OEt 2MeCN, 0 °C, 99%tricycliccompoundOHO 2CCO 2HRuCl 3·nH 2O NaIO 4MeCN-CCl 40 °CS. Nagumo et al ., Tetrahedron Lett., 43, 5333 (2002)OMeOHCMe1) TMSC(Li)N 2,THF –78 °C to rt, 71%2) Bu 3SnCu(Bu)CNLi 2 THF, –78 °C; MeI, DMPU –78 °C to rt 3) I 2, Et 2O, 0 °C 80% (2 steps)C 11H 17IO1) vinyl magnesium bromide Pd(PPh 3)4, PhH, 70 °C 88%2) H 2, CO, Rh(acac)(CO)2 (S, R )-BINAPHOS PhH, 30-35 °C, 20 atm 3) CrCl 2, CHI 3, THF 72% (2 steps)OMeMeMeIMeE. N. Jacobsen et al., J. Am. Chem. Soc., 123, 10772 (2001)OMeLi THF, MW 120 °C;DMP CH 2Cl 2, 0 °C75%F. Serratosa, Acc. Chem. Res., 16, 170 (1983)D. C. Harrowven et al., Angew. Chem. Int. Ed., 46, 425 (2007)O t -But -BuO 1) benzene reflux, quant2) NBS, CCl 4 83%C 12H 18O 4C 10H 18O 2OMeO OO t -Bu 1) MeLi (1.05 eq) THF, –78 °C; TFAA, 82%2), THF 37% (dr = 3:2)N H N thionyl chloride (theoretically 1 eq)CH 2Cl 2,–10 °C to rt;filtration;NH 2MgBrN HMeMetoluene reflux 51%(1 eq)THF 96%96%Kim, Y. H. et al. Tetrahedron Lett. 26, 3821 (1995)Julia, S. A. et al. Tetrahedron Lett. 27, 837 (1996)(as 4 eq)* theoretical amount54123N HP. S. Baran et al., Nature , 446, 404 (2007)H NCMe 1) t -BuOCl (1.2 equiv) CH 2Cl 2, –78 °C;prenyl 9-BBN (2 equiv) –78 °C 60%2) h υ, Et 3N (xs) PhH, rt 41%(63% based on RSM)N HH NCMe Bprenyl 9-BBN:C 8H 8O 3isovanillin1) allyl bromide K 2CO 3, acetone reflux, 8 h, 92%2) 180º C, decalin 5 h, 95%3) MeI, K 2CO 3 acetone, reflux 8 h, 83%C 12H 14O 34) acrylonitrile, DABCO H 2O, rt 3-5 days 67%5) Grubbs' 2nd gen. (5 mol%) 0.05 M CH 2Cl 2, rt 5-8 h, 90%CNOCH 3H 3COE. Wang et al., Tetrahedron, 63, 2824 (2007)BocNSMeOOC1)105 ºC, 45h 2) Pb(OAc)4 (2.2 eq), benzene, reflux 3) NaOAc, MeOHN NCOOMe MeOOC BocNSMeOOCOH R. B. Woodward et al., J . Am . Chem . Soc ., 88, 852 (1966)MeMeOn BuOOOHHH n Bu1) MgBr(CH 2)2Br, THF, 1.5 h, 92%2) TsOH, acetone, reflux 11 h, 82%3) NH 2NH 2, KOH, HO(CH 2)2OH110 to 190 °C, 8 h 4) O 3, EtOAc, –78 °C, 4 h; PPh 3, overnight 51% (2 steps)D. Kim et al., J. Org. Chem., 65, 4846 (2000)Br OO OHHO O OOH H HOTBS 1) i BuO 2CCl Et 3N, Et 2O; CH 2N 2, Et 2O 0 °C to rt, 81%2) Cu(CF 3COCHCOCF 3)2CH 2Cl 2, reflux, 96%1) PhNTf 2 NaHMDS THF, –78 °C2) CH 2=C(OEt)SnBu 3 Pd(PPh 3)4, LiCl THF, reflux 3) methyl vinyl ketone toluene, reflux 67% (3 steps)bicyclic compoundO OH HOTBS EtOH J. S. Clark et al., Angew. Chem. Int. Ed., 46, 437 (2007)54123E. J. Enholm et al., J. Org. Chem., 55, 324 (1990)Ph 3P CH 3Brn -BuLi (1 eq)THF 0 °C to rt;On -BuLi (1 eq)cyclohexanone −23 °C to rt56%C 11H 18OCHOKH (1.3 eq)18-crown-6THF, reflux 76%OHOMe S OPh OOMe+TFAA (1.5 eq)CH 3CN −40 ºC 83%OMeOHCOMeOOC 23H 20O 4S1) m CPBA (1 eq) 98%2) n -BuLi (5 eq) THF, −78 ºC; DMF (5 eq) 56%Y. Kita et al., Org. Lett., 2, 2279 (2000)ON 3BF 3⋅OEt 2, O 2–78 to 0 ºC 40%tetracyclic compoundC 12H 17NO 3H 2, Pd/C THF 77%NO HOH HF. G. West et al., Org. Lett., 9, 703 (2007)OCHO MeMeNHOHDMAD rt 85%PhMe, reflux50%O NH HMeCO 2Me OCO 2Me Me S. Kanemasa et al., Chem. Lett., 797 (1984)OOH CNBzOPhI(OAc)2 (1.5 eq)I 2 (1.0 eq), h νbenzene1) conc. HCldioxane, 40 °C 2) (COCl)2, cat. DMF benzeneNOHSPy, DMAP, O 2toluene, 80 °C;P(OMe)3O O OHBzOS. Hatakeyama et al ., J . Am . Chem . Soc ., 116, 4081 (1994)。

1342HO 2C H 2NHNO N 3Tf CuSO 4aq. K 2CO 3CH 2Cl 2MeOH 99 %HSPPh 2BH 3DCC CH 2Cl 298 %DABCO THF H 2O 70 °C 80%J. H. van Maarseveen et al ., Angew. Chem. Int. Ed., 42, 4373 (2003)Y. Hayashi et al., J. Org. Chem., 69, 5966 (2004)H. Yamamoto et al., Synlett , 705 (2006)OOOL-Proline (5 mol%)PhNODMF86%, >99%eeONHPhOOOONHPhO+EuCl 3 (30 mol%)EtOH 105 °C43%OHO 2STMSCr(CO)3TMSOTBSHHTsO1) t-BuOKDMSO, 0 °C 78%2) KBH 4MeOH, 0 °C 3) TBSCl imidazole DMF, rt80% (2 steps)h ν, Cl(CH 2)2Cl;evaporation;CO, MeOH 70%t-BuOK THF, –105 °C;NCS (1 eq), rt;t-BuOK, –105 °C;–105 °C to rt60%J. H. Rigby et al ., J. Am. Chem. Soc ., 121, 8237 (1999)PhOBr1) PPh 3, phenol 90 °C, 48 h 2) EtOAc, reflux 24 h1) NaHMDS (4 eq) THF, –78 °C; PhCHO, 90%2) t -BuOK rt, 2 h, 60%PhCCl 3CO 2H CCl 3CO 2Na MeCN, 95%salt A (MW < 400)P. L. Fuchs et al., J. Am. Chem. Soc. 126, 14314 (2004)1342W. Oppolzer et al ., Tetrahedron Lett., 27, 5471 (1986)ClMg (5 equiv), THF –65 °C → rt → 65 °C;CuI (1.1 equiv)TMEDA (3 equiv)–65 to –40 °C;(0.95 equiv)–78 °C76%CO 2MeC 16H 26O 21) NaOHMeOH-H 2O, 65 °C 100%2) (COCl)2 toluene, rt 3) i -Pr 2NEttoluene, reflux 57% (2 steps)H H OMe dr = 3:1NBnO NCEtOMeCO 2MeTMSOTf, EtNO 274%1) Pd/Cmesitylene 98%2) NaOH, EtOH/H 2O (1:1) reflux 75%N HNBnO EtBrian L. Pagenkopf et al ., Org. Lett ., 10, 157 (2008)CO 2MeOO OEt OTMSZnCl 2, Et 2O CuBr·SMe 2HMPA, THF83%h νhexane 95%1) 10% HCl aq.2) (imid)2CS DMAP, THF 85% (2 steps)OHOCO 2Men Bu3SnHAIBNbenzene reflux 92%Tetracyclic CompoundM. T. Crimmins et al., Tetrahedron Lett., 37, 8703 (1996)OOHO Me1) PhI, CO, CO 2 Et 3N, Pd(PPh 3)4 100 °C, 79%2) BBr 3, CH 2Cl 2 95%OBn1) o -NO 2C 6H 4SeCN P(n-Bu)3, THF, 90%2) H 2O 2, THF, 85%O OOO PhMeK. C. Nicolaou et al., J. Am. Chem. Soc ., 130, 11114 (2008)1342NMeS Et 2NO S h υhexane reflux74%**mixture of two stereoisomersPh 2O reflux89%PhLi, 0 °C, THF;aq. NaOH 66%NMePhOR. S. Grainger et al., J. Org. Chem., 73, 8116 (2008)MeOOPOCl 3 (12.0 eq.)DMF 80 °C 20 min 69%POCl 3 (12.0 eq.)DMF 120 °C 20 min 78%MeOCHOClClMeOOOClM. Shi et al., J. Org. Chem., 73, 8317 (2008)Ti(O i -Pr)4 (0.1 equiv.)EtMgBr (4 equiv.)THF-Et 2O (4:1)51%PhCHO, Na 2SO 4Al(OTf)3 (0.3 equiv.)CH 2Cl 2, –10 °C;TiCl 4 (1 equiv.)55%OOPhOHCO 2EtK. E. O'Neil et al ., Org. Lett ., 7, 515 (2005)OTBS1) nBuLi (2.2 eq),THF, -78o C to rt ; ICH 2CH(OCH 3)2* HMPA, -78o C to rt, 81%2) TBAF, THF, 90%3) BocNHTs, PPh 3, DEAD, THF, 89%4) HCl, MeOH, 85%1) LHMDS (3.0 eq), nBu 3SnCl THF, 0o C, 66%2) PhI +CN -OTf, CH 2Cl 2, -40 o C ; tBuOK, THF, -40 o C 56%N TsOCH 3K. S. Feldman et al., . Chem., 61, 5440, (1996)* theoretical amount: 1 eq.。