Claisen-rearrangement-mediated ring contraction of macrocyclic lactones. A new approach to carbocycles and heterocycles

Raymond L. Funk; Matthew M. Abelman; John D. Munger

doi:10.1016/S0040-4020(01)90572-1

Claisen-rearrangement-mediated ring contraction of macrocyclic lactones. A new approach to carbocycles and heterocycles

Raymond L. Funk, Matthew M. Abelman, John D. Munger

Chemistry

Research output: Contribution to journal › Article › peer-review

58 Scopus citations

Abstract

Macrocyclic ketene acetals 3 undergo Claisen rearrangements smoothly and constitute a viable and general approach to hetero- or carbocyclic ring systems 4. This novel ring contraction process is subject to high internal asymmetric induction (cf. lactones 7 → carbocycles 8) as well as relative asymmetric induction in the rearrangements of ketene acetals derived from lactones 18, 23 and 27. Finally, N-benzoylmeroquinene methyl ester (37) was prepared to demonstrate the potential of this methodology in heterocycle synthesis.

Original language	English (US)
Pages (from-to)	2831-2846
Number of pages	16
Journal	Tetrahedron
Volume	42
Issue number	11
DOIs	https://doi.org/10.1016/S0040-4020(01)90572-1
State	Published - 1986

All Science Journal Classification (ASJC) codes

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/S0040-4020(01)90572-1

Cite this

@article{0403c73276ec487abfd8290acab0a28f,

title = "Claisen-rearrangement-mediated ring contraction of macrocyclic lactones. A new approach to carbocycles and heterocycles",

abstract = "Macrocyclic ketene acetals 3 undergo Claisen rearrangements smoothly and constitute a viable and general approach to hetero- or carbocyclic ring systems 4. This novel ring contraction process is subject to high internal asymmetric induction (cf. lactones 7 → carbocycles 8) as well as relative asymmetric induction in the rearrangements of ketene acetals derived from lactones 18, 23 and 27. Finally, N-benzoylmeroquinene methyl ester (37) was prepared to demonstrate the potential of this methodology in heterocycle synthesis.",

author = "Funk, {Raymond L.} and Abelman, {Matthew M.} and Munger, {John D.}",

note = "Funding Information: 2t3402,0 92,1 6281, 4401, 3401. 1451, 005,915,780.725,700a s the major product.T his compoundw as identicalt o the cm{\textquoteright} ; {\textquoteleft}H-NMR (90 MHz, CDCI,) d 7.37( s, SH), 5.98553 majorp roducto btainedf rom thet reatmenotf them ixtureo f (m. IH),5.23@,I H),5.3&4.9O(m.2H).4.37-3.05(brm,4H), acids2 4a ndU with 1.C HIN2 ; 2. Or, MerS. 2.87-2.46(brm,2H),2.13-1.54(brm,2H). ( f )-N-BenzoyImeroquinemrteet hyle ster( 37).T he crude diazoketone(90.0mg,0.318tnmo1)wasdissolvedinMeGH(20 ml)andt o thissolnw asaddedasuspensionofAgbettxoa1t.e0( g, 4.37m mol,p reviouslyd riedat 25”. 0.01m mHg,1 2I t) and Et,N (lOml,7 1.7t tuuol)andth er esultanst olns tirreda t room lEJ. P. Shaefera nd J. J. BloomfieldO. rg. React. (N.Y.) 15. 1 tetnpf or 6 h. The mixturew asp ouredi nto CH,Cl, (100m l) (1967)*;J . J. Bloom6eldD, . C. Owsleya ndJ . M. Nelke,O rg. and washedw ith loO/,H CI aq (2 x 20 ml), Hz0 (20m l), sat React. (N. Y.) 23,259 (1976){\textquoteleft};P . R. Storya ndP. Busch,A do. NaHCO, aq (2x20 ml). brine, and dried (MgSO,). Org. Chem. 8.67( 1972);{\textquoteleft}J.E. McMurry, AccrsC lremR. es. Evaporationo f the solventsg ave7 5m g of an oil, whichw as 16,4 05( 1983){\textquoteleft};A . Maercka, Org. React. (N.Y.) 14, 270 purified by HPLC (Beckman-AltexU ltrasphereCyan0 (1965); K. B. Becker, Terrahedron36,17(1179 80). HPLC column,d p 5, id. 10 mm x 25 cm. using isopropyl ZFor a preliminarya ccounto f this work, see: {\textquoteleft}M. M. alcohol-hcxanes1, ~9f,l ow rate 4 ml tttin-{\textquoteleft}, retentiont ime Abelman,R . L. Funk and J. D. MungerJ r., J. Am. C/tent. 10.5m in)t o give7 0.5m g (77%)o f a clearo il. 1R (film)3 050, Sot. 104.403(01 9821{\textquoteleft}R: . L. Funk andJ . D. MunnerJ r.. J. 2990,2 9202, 845,1 732,1 630,1 575,1 492,1 435,1 365.1 310, Org.C &t. 49,{\textquoteleft}4319{\textquoteright}(198{\textquoteleft}4R).; L. Funk and J. DrMunger 12901, 2601, 2001, 1651, 1401, 0701, 005,920,7857,2 5,695 Jr., J. Org.C /tentS. o,7 07( 1985). cm-{\textquoteleft};{\textquoteleft}H-NMR(360MHz.CDCl~)67.37(~.5H),5.83(ddd.J {\textquoteleft}For reviewso n the Claisen rearrangemenst,e e: {\textquoteleft}S. J. = 16.50.10.43,8.48Hz.,lH),5.254.86(brm,2H).4.744.4O(bRrh oadsandN.R.Raulins,0rg.React.(N.I!)22,1(1975);*F. m, lH), 3.67(s ,3 H),3 .44-2.76(bmr ,Z H),2 .59-2.0(7b r m, 5H), Ziegler,A ccts Chem.R es. 10,2 27( 1977){\textquoteleft};G . B. Bennett, 1.87-134(brm , 2H); {\textquoteleft}sC-NMR (50.31M Hz, CDCI,, 50”) d Synrhesi5s 89( 1977). 172.761, 70.861. 36.211.3 4.511, 29.411,2 8.281, 26.971, 18.24, “S. DanishefskyR, . L. Funk and J. R. Kerwin Jr.. J. Am. 51.414. 2.673, 7.263, 5.692, 7.51;M S m/z (rel. int.) M{\textquoteright} 287 C/tern. Sot. lO$ 6889( 1980);* S. Danishefskya nd K. (3.61)2. 86(4.052),4 6( 2.19)2. 14( 4.99)1, 82( 10.59)1. 68( 2.56). Tsuxuki,Ib id. 102.6891 (1980)F.o r recente xploitationo f 148(1.851.134(1.361105(100.01.82(1.02b77(23.981.51th(1is. 8m7e)t.h odologys,e e:{\textquoteleft} M. J. BegleyA, . G. Camerona nd Exact m{\textquoteright}asst alc for C,;H,,G,N {\textquoteleft}(M{\textquoteright}j: 287.1521f;o und: D. W. Knight, J. Chem.S ot. C/tentC. ommw.8 27( 1984); 287.1517.ThesespectraIdwaetare identicatlo thoseobtained {\textquoteleft}R. K. Brunner and H.-J. Borschber,H e/u. Chfm. Acra from an authentics amplep rovidedb y Dr M. Uskokovic.I n 66, 2608( 1983){\textquoteleft};S . D. Burke,D . M. Armisteada nd F. J. addition,m obilitieso n TLC platesw erec ompareda ndf ound SchoenenJ.. Ora. Chem4. 320( 1984)?: I. D. Burke.D . M. to be identicalf or the follo~winsgo lvents ystems:E tOAc-Armisteada ndj. M. Fevig, kena&dron L&t. 26, 1163 hexanes.I : I. R, 0.35; Et,O. R, 0.56; isopropyl alcohol-(1985). hexan& 1:9, R,{\textquoteleft}0.40. _ {\textquoteright} . _ _ {\textquoteleft}-L. A. PaquetteJ., A. ColapretD, . R. Andrews,J.O rg.C &-m. ( fkMethy1 cis - N - benroyl - 3 - erheny-l 4 - piperidine 50, 201( 1985)*; W. C. Still, J. Am. Gem. Sot. 101,2 493 cmboxylareT. o the crudeh ydrolysisp roduct( k) - cis - N - (1979){\textquoteleft};S . L. Schreibera nd C. Sautini,J . Am. Chem.S ot. benxoyl - 3 - ethenyl - 4 - piperidinecarboxylaicc id( 97m g)w as 106.4038 (1984). addedd ry Et,0 (5m l)a ndt hem ixturew asc ooledt o 0” anda 6R . E. Ireland,R . H. Muellera ndA . K. Willard,J . Am.C /tent. solnofdiazomcthaneinEt,O(ca1 MinEt,O,5tnl)wasadded Sot. 98.2868(1 976). dropwisea nds tirredf or 30m in.T hee xcesds iazomethanwc as {\textquoteleft}S. J. Rhoads,R . D. Cockroft,J . Am. C)temS.ot.91.3126 removedin oacuoa ndt her esiduep assedth rougha shortp lug (1969). of silicag ela nds ubjectedto HPLC analysisa ndpurification s For a reviewo n the preparationo f macrolideas,e e: {\textquoteleft}T. (Beckman-AltcxU ltrasphere-Scio lumn,dp5 ,i .d. 10 nun x 25 MukaiyamaA, nger. Chem.I nr. Ed. Engl. 18. 707 (1979); cm, elution with 1: 1 EtOAc-hexanes)T. he minor fraction %. C. Nimlaou, Terrahedron 33.683 (1977)5;. Masamune, (retention time 1.25 mitt) gave 17.5 mg of t-butyl G. S. Batesa ndJ . W. Corcoran.A ttgewC. hemI.n c.E d. Engl. dimethylsilanoTl.h e majorf raciion( retention& e 5.44n &t) 16,585(1 977)F.o r ahemativew ayst o preparem acrolides. afforded6 8.5m a of an oil. IR (lilm) 30603. 0002. 940.2845. see:{\textquoteleft} R.-G. Carbon. J. H.-A. H&r and D. E. Henton,J . 1732.1 630,1 575.1 4901, 430,i3 70; 13251; 305;1 250,1 190; Chem.S ot. C/ternC. ommun2. 23( 1973)l: R . C. Cookson 1170,1150,1045.1015.995,920,78~700cn-{\textquoteright};{\textquoteleft}H-NMR(360a nd V. Bhat,J . Chem.S ot. Ch& Co&mm. 1123( 1981); MHz.CDCl,)67.38(brs,5H),5.83(ddd.=J 17.21.10.47.7.93 {\textquoteleft}R. C. Cookson and P. S. Ray, Terra/tedroLne tr.2 3.3521 Hz, lH), 5.334.94( m. 2H), 4.60-4.31(m . lH), 3.92-3.7(3m , (1982)P; K. Kostova and M. Hesse,H elu. C&n. Acfa 66, lH), 3.63( s. 3H). 3.493.16(m , ZH), 3.02-2.6(8m , 2H), 2.18-741(1983);*Y.NakashitaandM.Hesse,lbid.66,845(1983); 1.54(m ,2 H). {\textquoteleft}N. Ono,.H. Miyake and A. Kaji, J. Org. Chin. 49,4997 (19841{\textquoteleft}E:. Vedeis. Accts Chem. Res. 17. 358 (1984); {\textquoteleft}E. J. Acknowledgement-We appreciatteh ef inanciaal ndm aterial Corey; D. J. Bt&elle and K. C. Nicolaou.; . Am: Gem. supportp rovidedb y theN ationalI nstituteso f Health( Grant Sot. 99,7359 (1977){\textquoteleft};A . EscheumoseMr, . Shibuyaa nd F. No. BM2866301). High-field( 360M Hz) rH-and “C-NMR Jaisli, Angew.C hem Inr. Ed. Engl. 1%6 36( 1979)“;S . L. spectraw ereo btainedo na spectrometepru rchasewd ithf unds Schreibera nd W.-F. Liew, J. Am. Chem.S ot. 107,2 950 providedi,n part,b y theN ationalS cienceF oundation( Grant (1985a) nd refsc itedt herein. No. CHE-80-24328M).a sss pectraw ereo btainedt hrought he 9F or a definitiono f thist erm,s ee:P . A. BartlettT, etrahedron National ScienceF oundationR egionalM ass Spectroscopy 36.2( 1980). Centera t the Universityo f Nebraska( Grant No. CHE-82-LoT.Mukaiyama,M.UsuiandK.Saigo,Chem.Lett.49(l976). 11164).W e also thank Professor Wolinsky. Purdue ” W. C. Still and 1.G alynker.T etrahedro3n7 ,3981(1981). University,forspectrao+f() -dihydronepetalactone(%),and Is D. E. Ames,A . N. Covella ndT . G. Goodbum.J . C/ternS. ot. Dr Uskokovico f Hoffmann-La RocheI nc. for an authentic 5889( 1963). sampleo f N-benxoylm eroquinenme ethyle ster( 37). “P. H. J. Carlsen. R. Katsuki. V. S. Martin and K. B. SharplessJ,. Org. Chem4 6.3936(1 981). Nore a&d in proof-The stereochemicaals signmentfso r {\textquoteleft}*D. E. Jamesa nd J. K. Stille,J . Org. C/tent4. 6.3936(1 981). cyclopentanecarboxyalicci ds2 4a nd 25h aveb eenc ontirmed i%J. Wolinsky,D . Dickerson,M . SlabaughD, . Nelson,T . bya ni ndependensty nthesisT. hus,s ubjectiono f 3-isobutoxy-SakattS, . Hoe,S . B. Hyeasa ndR. KatsumuraT, etrahedron Zcyclopentenl--one to the followings ynthetics equenc:e I. L.err.4 6. 4097 (1965);* I. Fleming and N. K. Terre& ZLDA; 2. CH,C(CHrCI),; 3. CoCI,, NaBH,; 4. MeLi; 5. TetrahedronL etr. 5103( 1984);{\textquoteleft}J . Wolinsky and E. J. H,O{\textquoteright}; 6. RuCl,, NaIO,; 7. CHrNr affordedt hea ll-& isomer EustaceJ,. Org.C /tent3. 7.3376(1 972). of methyl 2-(I -oxoethyl)+methylcyclopentanecarboxylatte6 Authentics pectraw ere kindly providedb y ProfessorJ .",

year = "1986",

doi = "10.1016/S0040-4020(01)90572-1",

language = "English (US)",

volume = "42",

pages = "2831--2846",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "11",

}

TY - JOUR

T1 - Claisen-rearrangement-mediated ring contraction of macrocyclic lactones. A new approach to carbocycles and heterocycles

AU - Funk, Raymond L.

AU - Abelman, Matthew M.

AU - Munger, John D.

N1 - Funding Information: 2t3402,0 92,1 6281, 4401, 3401. 1451, 005,915,780.725,700a s the major product.T his compoundw as identicalt o the cm’ ; ‘H-NMR (90 MHz, CDCI,) d 7.37( s, SH), 5.98553 majorp roducto btainedf rom thet reatmenotf them ixtureo f (m. IH),5.23@,I H),5.3&4.9O(m.2H).4.37-3.05(brm,4H), acids2 4a ndU with 1.C HIN2 ; 2. Or, MerS. 2.87-2.46(brm,2H),2.13-1.54(brm,2H). ( f )-N-BenzoyImeroquinemrteet hyle ster( 37).T he crude diazoketone(90.0mg,0.318tnmo1)wasdissolvedinMeGH(20 ml)andt o thissolnw asaddedasuspensionofAgbettxoa1t.e0( g, 4.37m mol,p reviouslyd riedat 25”. 0.01m mHg,1 2I t) and Et,N (lOml,7 1.7t tuuol)andth er esultanst olns tirreda t room lEJ. P. Shaefera nd J. J. BloomfieldO. rg. React. (N.Y.) 15. 1 tetnpf or 6 h. The mixturew asp ouredi nto CH,Cl, (100m l) (1967)*;J . J. Bloom6eldD, . C. Owsleya ndJ . M. Nelke,O rg. and washedw ith loO/,H CI aq (2 x 20 ml), Hz0 (20m l), sat React. (N. Y.) 23,259 (1976)‘;P . R. Storya ndP. Busch,A do. NaHCO, aq (2x20 ml). brine, and dried (MgSO,). Org. Chem. 8.67( 1972);‘J.E. McMurry, AccrsC lremR. es. Evaporationo f the solventsg ave7 5m g of an oil, whichw as 16,4 05( 1983)‘;A . Maercka, Org. React. (N.Y.) 14, 270 purified by HPLC (Beckman-AltexU ltrasphereCyan0 (1965); K. B. Becker, Terrahedron36,17(1179 80). HPLC column,d p 5, id. 10 mm x 25 cm. using isopropyl ZFor a preliminarya ccounto f this work, see: ‘M. M. alcohol-hcxanes1, ~9f,l ow rate 4 ml tttin-‘, retentiont ime Abelman,R . L. Funk and J. D. MungerJ r., J. Am. C/tent. 10.5m in)t o give7 0.5m g (77%)o f a clearo il. 1R (film)3 050, Sot. 104.403(01 9821‘R: . L. Funk andJ . D. MunnerJ r.. J. 2990,2 9202, 845,1 732,1 630,1 575,1 492,1 435,1 365.1 310, Org.C &t. 49,‘4319’(198‘4R).; L. Funk and J. DrMunger 12901, 2601, 2001, 1651, 1401, 0701, 005,920,7857,2 5,695 Jr., J. Org.C /tentS. o,7 07( 1985). cm-‘;‘H-NMR(360MHz.CDCl~)67.37(~.5H),5.83(ddd.J ‘For reviewso n the Claisen rearrangemenst,e e: ‘S. J. = 16.50.10.43,8.48Hz.,lH),5.254.86(brm,2H).4.744.4O(bRrh oadsandN.R.Raulins,0rg.React.(N.I!)22,1(1975);*F. m, lH), 3.67(s ,3 H),3 .44-2.76(bmr ,Z H),2 .59-2.0(7b r m, 5H), Ziegler,A ccts Chem.R es. 10,2 27( 1977)‘;G . B. Bennett, 1.87-134(brm , 2H); ‘sC-NMR (50.31M Hz, CDCI,, 50”) d Synrhesi5s 89( 1977). 172.761, 70.861. 36.211.3 4.511, 29.411,2 8.281, 26.971, 18.24, “S. DanishefskyR, . L. Funk and J. R. Kerwin Jr.. J. Am. 51.414. 2.673, 7.263, 5.692, 7.51;M S m/z (rel. int.) M’ 287 C/tern. Sot. lO$ 6889( 1980);* S. Danishefskya nd K. (3.61)2. 86(4.052),4 6( 2.19)2. 14( 4.99)1, 82( 10.59)1. 68( 2.56). Tsuxuki,Ib id. 102.6891 (1980)F.o r recente xploitationo f 148(1.851.134(1.361105(100.01.82(1.02b77(23.981.51th(1is. 8m7e)t.h odologys,e e:‘ M. J. BegleyA, . G. Camerona nd Exact m’asst alc for C,;H,,G,N ‘(M’j: 287.1521f;o und: D. W. Knight, J. Chem.S ot. C/tentC. ommw.8 27( 1984); 287.1517.ThesespectraIdwaetare identicatlo thoseobtained ‘R. K. Brunner and H.-J. Borschber,H e/u. Chfm. Acra from an authentics amplep rovidedb y Dr M. Uskokovic.I n 66, 2608( 1983)‘;S . D. Burke,D . M. Armisteada nd F. J. addition,m obilitieso n TLC platesw erec ompareda ndf ound SchoenenJ.. Ora. Chem4. 320( 1984)?: I. D. Burke.D . M. to be identicalf or the follo~winsgo lvents ystems:E tOAc-Armisteada ndj. M. Fevig, kena&dron L&t. 26, 1163 hexanes.I : I. R, 0.35; Et,O. R, 0.56; isopropyl alcohol-(1985). hexan& 1:9, R,‘0.40. _ ’ . _ _ ‘-L. A. PaquetteJ., A. ColapretD, . R. Andrews,J.O rg.C &-m. ( fkMethy1 cis - N - benroyl - 3 - erheny-l 4 - piperidine 50, 201( 1985)*; W. C. Still, J. Am. Gem. Sot. 101,2 493 cmboxylareT. o the crudeh ydrolysisp roduct( k) - cis - N - (1979)‘;S . L. Schreibera nd C. Sautini,J . Am. Chem.S ot. benxoyl - 3 - ethenyl - 4 - piperidinecarboxylaicc id( 97m g)w as 106.4038 (1984). addedd ry Et,0 (5m l)a ndt hem ixturew asc ooledt o 0” anda 6R . E. Ireland,R . H. Muellera ndA . K. Willard,J . Am.C /tent. solnofdiazomcthaneinEt,O(ca1 MinEt,O,5tnl)wasadded Sot. 98.2868(1 976). dropwisea nds tirredf or 30m in.T hee xcesds iazomethanwc as ‘S. J. Rhoads,R . D. Cockroft,J . Am. C)temS.ot.91.3126 removedin oacuoa ndt her esiduep assedth rougha shortp lug (1969). of silicag ela nds ubjectedto HPLC analysisa ndpurification s For a reviewo n the preparationo f macrolideas,e e: ‘T. (Beckman-AltcxU ltrasphere-Scio lumn,dp5 ,i .d. 10 nun x 25 MukaiyamaA, nger. Chem.I nr. Ed. Engl. 18. 707 (1979); cm, elution with 1: 1 EtOAc-hexanes)T. he minor fraction %. C. Nimlaou, Terrahedron 33.683 (1977)5;. Masamune, (retention time 1.25 mitt) gave 17.5 mg of t-butyl G. S. Batesa ndJ . W. Corcoran.A ttgewC. hemI.n c.E d. Engl. dimethylsilanoTl.h e majorf raciion( retention& e 5.44n &t) 16,585(1 977)F.o r ahemativew ayst o preparem acrolides. afforded6 8.5m a of an oil. IR (lilm) 30603. 0002. 940.2845. see:‘ R.-G. Carbon. J. H.-A. H&r and D. E. Henton,J . 1732.1 630,1 575.1 4901, 430,i3 70; 13251; 305;1 250,1 190; Chem.S ot. C/ternC. ommun2. 23( 1973)l: R . C. Cookson 1170,1150,1045.1015.995,920,78~700cn-’;‘H-NMR(360a nd V. Bhat,J . Chem.S ot. Ch& Co&mm. 1123( 1981); MHz.CDCl,)67.38(brs,5H),5.83(ddd.=J 17.21.10.47.7.93 ‘R. C. Cookson and P. S. Ray, Terra/tedroLne tr.2 3.3521 Hz, lH), 5.334.94( m. 2H), 4.60-4.31(m . lH), 3.92-3.7(3m , (1982)P; K. Kostova and M. Hesse,H elu. C&n. Acfa 66, lH), 3.63( s. 3H). 3.493.16(m , ZH), 3.02-2.6(8m , 2H), 2.18-741(1983);*Y.NakashitaandM.Hesse,lbid.66,845(1983); 1.54(m ,2 H). ‘N. Ono,.H. Miyake and A. Kaji, J. Org. Chin. 49,4997 (19841‘E:. Vedeis. Accts Chem. Res. 17. 358 (1984); ‘E. J. Acknowledgement-We appreciatteh ef inanciaal ndm aterial Corey; D. J. Bt&elle and K. C. Nicolaou.; . Am: Gem. supportp rovidedb y theN ationalI nstituteso f Health( Grant Sot. 99,7359 (1977)‘;A . EscheumoseMr, . Shibuyaa nd F. No. BM2866301). High-field( 360M Hz) rH-and “C-NMR Jaisli, Angew.C hem Inr. Ed. Engl. 1%6 36( 1979)“;S . L. spectraw ereo btainedo na spectrometepru rchasewd ithf unds Schreibera nd W.-F. Liew, J. Am. Chem.S ot. 107,2 950 providedi,n part,b y theN ationalS cienceF oundation( Grant (1985a) nd refsc itedt herein. No. CHE-80-24328M).a sss pectraw ereo btainedt hrought he 9F or a definitiono f thist erm,s ee:P . A. BartlettT, etrahedron National ScienceF oundationR egionalM ass Spectroscopy 36.2( 1980). Centera t the Universityo f Nebraska( Grant No. CHE-82-LoT.Mukaiyama,M.UsuiandK.Saigo,Chem.Lett.49(l976). 11164).W e also thank Professor Wolinsky. Purdue ” W. C. Still and 1.G alynker.T etrahedro3n7 ,3981(1981). University,forspectrao+f() -dihydronepetalactone(%),and Is D. E. Ames,A . N. Covella ndT . G. Goodbum.J . C/ternS. ot. Dr Uskokovico f Hoffmann-La RocheI nc. for an authentic 5889( 1963). sampleo f N-benxoylm eroquinenme ethyle ster( 37). “P. H. J. Carlsen. R. Katsuki. V. S. Martin and K. B. SharplessJ,. Org. Chem4 6.3936(1 981). Nore a&d in proof-The stereochemicaals signmentfso r ‘*D. E. Jamesa nd J. K. Stille,J . Org. C/tent4. 6.3936(1 981). cyclopentanecarboxyalicci ds2 4a nd 25h aveb eenc ontirmed i%J. Wolinsky,D . Dickerson,M . SlabaughD, . Nelson,T . bya ni ndependensty nthesisT. hus,s ubjectiono f 3-isobutoxy-SakattS, . Hoe,S . B. Hyeasa ndR. KatsumuraT, etrahedron Zcyclopentenl--one to the followings ynthetics equenc:e I. L.err.4 6. 4097 (1965);* I. Fleming and N. K. Terre& ZLDA; 2. CH,C(CHrCI),; 3. CoCI,, NaBH,; 4. MeLi; 5. TetrahedronL etr. 5103( 1984);‘J . Wolinsky and E. J. H,O’; 6. RuCl,, NaIO,; 7. CHrNr affordedt hea ll-& isomer EustaceJ,. Org.C /tent3. 7.3376(1 972). of methyl 2-(I -oxoethyl)+methylcyclopentanecarboxylatte6 Authentics pectraw ere kindly providedb y ProfessorJ .

PY - 1986

Y1 - 1986

N2 - Macrocyclic ketene acetals 3 undergo Claisen rearrangements smoothly and constitute a viable and general approach to hetero- or carbocyclic ring systems 4. This novel ring contraction process is subject to high internal asymmetric induction (cf. lactones 7 → carbocycles 8) as well as relative asymmetric induction in the rearrangements of ketene acetals derived from lactones 18, 23 and 27. Finally, N-benzoylmeroquinene methyl ester (37) was prepared to demonstrate the potential of this methodology in heterocycle synthesis.

AB - Macrocyclic ketene acetals 3 undergo Claisen rearrangements smoothly and constitute a viable and general approach to hetero- or carbocyclic ring systems 4. This novel ring contraction process is subject to high internal asymmetric induction (cf. lactones 7 → carbocycles 8) as well as relative asymmetric induction in the rearrangements of ketene acetals derived from lactones 18, 23 and 27. Finally, N-benzoylmeroquinene methyl ester (37) was prepared to demonstrate the potential of this methodology in heterocycle synthesis.

UR - http://www.scopus.com/inward/record.url?scp=0000753416&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000753416&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(01)90572-1

DO - 10.1016/S0040-4020(01)90572-1

M3 - Article

AN - SCOPUS:0000753416

VL - 42

SP - 2831

EP - 2846

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 11

ER -

Claisen-rearrangement-mediated ring contraction of macrocyclic lactones. A new approach to carbocycles and heterocycles

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