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


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).
NaI, acetone reflux




X= Cl, Br, I

R Cl



- conversion of hydroxyl groups to halides:

Organic Reactions 1983, 29, 1

- 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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