sides the 0 " Ong 5sse5s @ Reactions which & tal as the electron source are AMONG methods Metal as the el wl jon of for reducing organic compounds, particularly those W/E sctio stem. Before idesy ; metals development of the metal hydride kali oe carbonyl groups by alkali metals was widely used. Reductions 7 he met cae known as es CUrS as red, on proceeds, sfer nsfer : ins with the {rans Dissolving metal reduction of a carbonyl group begins wi com of an electre " jon, ical anion, ‘on from the metal to the carbonyl group. A tadica’, to ac monly Known asa key » (s formed a3 the metal atom is oxidize ies which #8 Fe Protonation produces an electrically neutral free-radical see eaanon of duced to a Sarbanion by a second atom of the metal. A second p' evolution of the very basic earbase ene eer dite | &aseous hydrogen usally accompanies these reactions, reductiol to the Production of Molecular hydrogen. | OH I Nae Ha, CHCH,CCH, "5 O:-Nat OH J EL, CHYCH,CHCH, seater nedlectons em carried out in an alcohol or an amine medium (Sometimes liquid ammonia) so that the solvent can provide the re- diized proton. Aldehy ketones, and esters are readily reduced by this fnethod Fisolated double bonct ss wher estes, though conjugated double bonds casi be reduced by a De ie hich is essertally a radical 4g. ga addition, The carbonyl Siup is not reduce-t in this case i ee hydrogen to the tiple bon, baa cgay weet eee Proceeds sterecepecifcally bp way. This contrasts with the syn addition of catalytic hydroge, Cycioheptanad cA d of alkynes aut anti pack nation, Cyctoheptanone . ~ a "CH SCO, H, Avion, ™CoH,,.CHLOH Ely heplanoate Tepe Hig CH) CCICH,) CH, Bec ett Scanned with CamScannertadGtions §— 935 gee —_ is not readily avail- iion is stabilized or a proton source is not ily aval atthe! intermediate may occur. The dimerization nreactons in aprotic solvents and with metals, such as aluminum, ae ich form disalts. (These metals are commonly sed amalgam, the metalmercuty alloy.) The dimer is the Fy-diol. Protonation produces a pinacol. able, patti Zinc, and Mf Kt:O:- :0:-Kt 1H OH FiO, (CgHH,)gC —C(CoHsbe é (CyHy)p 2 (CoH oC oH) 2(CaiggE=O !-K* —> (CcHghhC+—+C (CH ae Oo OH scrylcrt, UMAMOIE MA, oy we! HO fm} PROBLEM 24-26 Suggest a mechanism for cach of ite following reactions: 1H H(CH,),CO,E1 SYEOH, a CH,(CH,),CH CH,(CH,), CH=CH(CH,),CH,OH 2 i \ umount, vA I~ cH, CH, OH OH i . © 2CgH,CCH{CH,), 2MY/GHs CoH —C— Cy, 2) 1,0 (CH,),CH CH(CH,), Esters unilergo a related reduction known as the acyloin reaction. The reaction product js an a-hydroxy ketone, an acyloin. This precess, when car- wed out with « diester, has been Patticularly useful for the synthesis of large cyclic structures, The diester is added very slowly to the rapidly stirring mix: ture of sodium metal in the hot solvent. Such Righ dilution is necessary to favor intramolecular cyclization rather than an intermolecular reaction, 1 Nafaylenefd ( Yeion i yHO CHO;C(CH,),CO,CH, Scanned with CamScanner