FUNCTIONAL GROUP INTERCONVERSIONS Functional Group Interconversions C&S Chapter 3 #1; 2; 4a,b, e; 5a, b, d; 6a,b,c,d; 8 1 2 3 4 5 6 7 sulfonates halides nitriles azides amines esters

and lactones amides and lactams

119

Sulfonate Esters - reaction of an alcohols (1° or 2°) with a sulfonyl chloride
R OH R'SO2Cl O R O S O sulfonate ester R' CF3 CH3 triflate tosylate R'= CH3 mesylate

- sulfonate esters are very good leaving groups. competing side reaction

Elimination is often a

Halides - halides are good leaving groups with the order of reactivity in SN2 reactions being I>Br>Cl. Halides are less reactive than sulfonate esters, however elimination as a competing side reaction is also reduced. - sulfonate esters can be converted to halides with the sodium halide in acetone at reflux. Chlorides are also converted to either bromides or iodides in the same fashion (Finkelstein Reaction).
O R O S O
NaI, acetone reflux

R'

X-

R X

X= Cl, Br, I

R Cl

R

I

- conversion of hydroxyl groups to halides:
R OH

Organic Reactions 1983, 29, 1
R X

- R-OH to R-Cl - SOCl2 - Ph3P, CCl4 - Ph3P, Cl2 - Ph3P, Cl3CCOCCl3

PBr3. pyridine TsCl.Dehydration of oximes R CHO H2NOH•HCl R N OH P2O5 H R C N . 2009 . 1309 . 1998. 39 . DEAD. 4907 Me Me2AlNH2 O O Ar H 3C NC Ar OH JOC 1987.displacement of halides or sulfonates with cyanide anion R X KCN. pyridine .FUNCTIONAL GROUP INTERCONVERSIONS 120 .Reduced to aldehydes with DIBAL.Ph3P.Ph3P.dehydration of amides O R NH2 R C N - POCl3.R-OH to R-Br . 52.Reaction of esters and lactones with dimethylaluminium amide TL 1979.Ph3P. MeI Nitriles .R-OH to R-I . DIBAL RC≡N RCHO . 18-C-6 DMSO R C N . CBr4 . pyridine P2O5 SOCl2 . Br2 .Oxidation of hydrazones O O N NMe2 (97%) C N Tetrahedron Lett.

reduction of nitro groups R NO2 H2.5 % ee) . H2O NaBH4 LiAlH 4 Zn. 5886 HO (PhO)2P(O)-N3 O DBU.activation of the alcohol R OH + + N Me TsO Ph3P. NaN3 EtO2C F + N Me R N3 OR + N Me O + PPh3 N N _ CO2Et R OH + EtO2C N N CO2Et DEAD + R O PPh3 activated alcohol R-OH R N3 + Ph3P=O N3 SN2 + DBU-H + JOC 1993.Gabriel Synthesis O N . 27.K+ O R X O N R O H2NNH2 R NH2 . 831 O 121 .6 % ee) Ar O O P(OPh)2 + N3 - (91 %) O (97. PhCH3 (99.Photolyzed to aldehydes Amines . Pd/C Al(Hg).FUNCTIONAL GROUP INTERCONVERSIONS Azides . Sn or Fe and HCl H2NNH2 sodium dithionite R NH2 .displacement of halides and sulfonates with azide anion O O SO2N(C6H11)2 O O SO2N(C6H11)2 NH2 HO NH2 LDA. 58. THF NBS O SO2N(C6H11)2 Br O NaN3 O SO2N(C6H11)2 N3 O TL 1986.

reduction of oximes (from aldehydes and ketones) N R H2.reduction of amides O R N R'' R' R N R'' R' H2.reduction of azides R N3 H2. Pd/C Raney nickel NaBH4. Pd/C B2H6 NaBH4 LiAlH 4 Zn. PtO 2/C B2H6 NaBH4 LiAlH 4 AlH3 Li. Pd/C B2H6 NaBH4.Curtius rearrangement O NaN3 R Cl R O •• •• N N N + ∆ . HCl (RO)3P Ph3P thiols OH NH2 R' R R' 122 R CH2 NH2 R NH2 . NH3 . TiCl4 LiBH4 LiAlH 4 AlH3 .reduction of nitriles R C N H2.N2 R NH2 R O •• N •• •• nitrene R N O isocyanate H2O . AcOH . TiCl4 LiAlH 4 Na(Hg).FUNCTIONAL GROUP INTERCONVERSIONS .

DMF R3N H 2N R N R R-N2 TsN3 R JOC 1995. DMF Pd(0).Diazoalkanes: carbene precursors R-CHO 1) NH2NH2 2) Pb(OAc)4. O R diazo ketone C O H ketene N2 hν ROH R O •• CH O Wolff Rearrangement R'OH R OR' O R CO2Me TsN3. DMF 110°C Tf N N N N Tf Na. 60. Int. 3321 + I2-KI H2O. 32. 48. 43. 1975. Et3N R O N2 . ROH CO2R TL 1985. 26 . Ed. 251 . 46 . NH3 Tf NH HN NH HN cyclam 123 TL 1992.Eschweiler-Clark Reaction . 1109 . 5505 Tf . Engl.Borsch Reaction . Chem.reductive aminations of aldehydes and ketones . 15. NaHCO3 O H O O I I O . 1970.alkylation of sulfonamides Tf N N HN HN Tf Tf Br Br Tf K2CO3. 33 .FUNCTIONAL GROUP INTERCONVERSIONS . 4725 N2 R . 570 Esters and Lactones .Reaction of alcohols with "activated acids" .Arndt-Eistert Reaction O R Cl CH2 N2 Et2 O R Angew. Chem. J.Baeyer-Villigar Reaction Organic Reactions 1993.Pd(0) catalyzed carboylation of enol triflates OTf CO.transaminiation O PhCH2NH2 H+ N Ph tBuOK N Ph H3O + NH2 Can.Halo Lactonizations CO2H review: Tetrahedron 1990.

Organic Reactions. air (86%) O O 124 JOC 1993. 5298 . 1 O R R' R O R R' N OH R' PCl5 R O R NR' O NR' . 1109 O O PhCH2NH2 AlMe3 OTHP OH O N H OTHP Ph TL 1977. 1148 . 35. 107 . 335 Mechanism: JACS 1988. 3815 DIBAL O R OR' H3CNH(OCH3) •HCl AlMe3 R O N OCH3 O R1-M R R1 R CH3 O H .Schmidt rearrangement HN3 H+ . 22. 1991. 6487 O DEAD. 4171 -Weinreb amide Tetrahedron Lett. 1981. 110 . Ph3P R''CO2H R O R' R'' Inversion of alcohol stereochemistry OH R R' Amides and Lactams . DMF Pd(0). 1.Selenolactonization PhSe O OH PhSeCl.reaction of an "activated acid" with amines . 58. 42.Mitsunobu Reaction Synthesis 1981 . R2NH NR2 TL 1985. CH2Cl2 O O H 2O 2 O O JACS 1985.FUNCTIONAL GROUP INTERCONVERSIONS Pd(OAc)2 (5 mol %) CO2H DMSO. 26 .others O OTf CO.Beckman Rearrangement Organic Reactions 1988.

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