The Synthesis of Optically Active Non-carbohydrate Compounds

The use of derivatives of L-ascorbic acid in attempts to synthesize the naturally occurring spirodilactones leucodrin and conocarpin is noted in Chapter 17. Efficient asymmetric induction has been accomplished through the photoaddition reactions of residues linked to D-mannitol as the chiral agent thus, the tetracinnamate derivative (468) underwent smooth intramolecular + 2ir) photocycloaddition to give cyclobutanes having the truxinic acid (head-to-head) 

Reagents i, (Me0)2P(0)CHaC0sMe ii, Hj-Ni iii, LiAlH4-THF iv, CrOj-py v, PhaP CH-(CH2)3C02Na vi, Hj-Pt-AcOH vii, CHaN -EtaO viii, DMSO-DCC-CFjCO H  

Reagents i, Vol. 3, p. 87 ii, BnOCOCl(CbzCl) iii, NaN,-DMF iv, H -Pd v, TsOH-HjO-dioxan vi, CrOs-AcOH vii, HBr-AcOH viii, NaOH ix, BrCN x, HCl xi, Dowex-50(NH4+) resin 

Reagents i, AcOH ii,TsCl-py iii, base iv, CjHiNLi-EtaO v, MsCl-py vi, NaNa vii, NalO vili, Bra-H O ix, H3O+ x, Pd-H, 

Reagents i, BuMgCl ii, AcjO-py iii, NBS-CCI4 iv, AgF-py v, Ha-Pd vi, AcaO-AcOH-HaSO, vii, MeONa viii, NalOi ix, MeOH-HCl x, MsCl-py xi, NaOBz-DMF xii, HsO+ xiii, Bta-HaO xiv, (MeaCHCHaCO)aOCl-py 

The use of 2,5-dicarbonyl sugars in the synthesis of heterocyclic compounds has been reviewed.  

Kagaku To Yakugaku No Kyoshitsu, 1975, 46, 12 (Chem. Abs., 1976, 84, 105 918t), S. Aburaki and M. Kinoshita, Ghent. Letters, 1976, 701. 

Reagents i, MeMgl ii, Ph3P=CH2 iii, Hg(OAc)2 iv, NaBH4 v, BnCl-NaH-DMF vi, H+ vii, AcaO-BFjjEtzOj viii, NaI04 ix, PhaP=CHCOMe x, Ha-Pd-C 

Reagents i, MeMgCEtjO ii, CrOg-MeaCO iii, Ph3P=CH2 iv, BaHe-THF v, HaOa-NaOH vi, TsCl-py vii, [CeHuN=CEtCHMe] viii, dil. HCl ix, g.l.c. 

Reagents i, NaBHj ii, TsCl-py iii, o-BnOCsHiOH-MeONa iv, HsO+ v, Hj-Pd-C vi, MeONa vii, EtjNH or piperidine 

A brief summary has appeared on the use of carbohydrate precursors for the synthesis of chiral acyclic, heterocyclic, and carbocyclic compounds. The reaction of monosaccharides (e.g. o-mannose) with benzene or toluene in liquid hydrogen fluoride yielded l,l,2-triaryl-l,2-dideoxyalditols [e.g. (658)] that were further transformed into condensed aromatic hydrocarbons [e.g. (659) and purpuricene (660)].  

A biomimetic synthesis of (+)-biotin methyl ester (665), involving stereospecific ring-closure to a tetrahydrothiophen system during the final stage, is shown in 

Knauel, F. Micheel, and M. Pesenacker, Amer. Chem. Soc. SymposiwH Ser., 1976,39 (Synthetic Methods for Carbohydrates Symposium), 227 (Chem. /4fcs., 1977,87,68 541d). 

Reagents i, MeC(OMe)2NMe2-diglyme-heat ii, KjCOj-MeOH iii, Ij-THF-HjO iv, BujSnH 

Reagents , NaNj-NH Cl ii, MsCl-py iii, Ac O-BFj EtjO iv, MeOH-HCl v, NaBH vi, MejC(OMe),-DMF-H vii, LiNj-DMF viii, Hj-Lindlar catalyst ix, COClj-Ca, X, ACjO-py xi, 80% AcOH xii, NaI04 xiii, PhjP=CHCH=CHC02Me-CH2Cl2 xiv, Hj-Pd-C XV, MeONa xvi, NajS-DMF. 

Reagents i, MegCuLi ii, AcaO-BFa iii, BujSnSEt-SnCIa iv, MeO v, Ni vi, TrCl-py  

Reagents i, CjHuMgBr-LijCuCU ii, MsCl-EtjN iii, CFaC0tH-H 0 iv, NaOMe V, CrOa-py vi, NH OH vii, BzCl-i y viii, MsQ-Pi NH ix, Ag 0-AgC10  

5-anhydro-L-idose 3,6-disulphonate ester derivative (9), prepared from D glucose in good yield, had been used to synthesize both D epiallomuscarine (10) and D-isoepiallomuscarine (11), both sequences involved the 3,4-anhydro-talose derivative formed from (9) which with lithium aluminium 

Approaches to the syntheses of segments of the macrolide ring in erythrono-lide A have been described, using o-glucose as the asymmetric source material (see also VoL 11, p. 231). 

The utilization of carbohydrates for the synthesis of chiral crown ethers has been further explored, giving derivatives with the general structures (12) and (13) using 4,-6-O-benzylidene derivatives of methyl a-o-galacto-, gluco-, and manno-pyranoside in a base-catalysed reaction with diethylene glycol bis-toluene-p-sulphonate.  

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The intensity of developments in this area can be gauged by the fact that the Specialist Periodical Reports (Carbohydrates) of the Chemical Society, beginning with Volume 9, now include a section on The Synthesis of Optically Active Non-Carbohydrate Compounds . 

Although references to the use of carbohydrates in the total synthesis of optically active non-carbohydrate compounds have been included in previous Reports, they were usually scattered throughout several chapters. Because of the growing interest in using carbohydrates in this way, such references have been collected together in a new chapter at the end of Part I. 

THE USE OF CARBOHYDRATES IN THE SYNTHESIS AND CONFIGURATIONAL ASSIGNMENTS OF OPTICALLY ACTIVE, NON-CARBOHYDRATE COMPOUNDS... 

Inch, T. D., The Use of Carbohydrates in the Synthesis and Configurational Assignments of Optically Active, Non-carbohydrate Compounds, 27, 191-225... 

Inch, T D, The use of carbohydrates in the synthesis and configurational assignment of optically active non-carbohydrate compounds, Adv. Carbohydr. Chem. Biochem., 27, 191-225, 1972. 

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