物理有机化学(第2版)

Theendofthetwentiethcentorymarksapproximatelyonecenturyofeffortinattemptingtounderstandthebasisofchemicalreactivityandthedetailedpathwaysofreactionsoforganiccompounds.Theresultcanbeviewedwithsomesatisfactioninthatbroadprincipleshavebeenestablishedandthemechanismsofalmostallreactionscannowbesaidtobeunderstoodinmodestdetail.Thesubjecthasadvancedintheeightyearssincethefirsteditionwaspublished.Inparticular,theavailabilityofyetmorepowerfulcomputershaspermittedreactionpathwaysofprocessessuchasDiels-Alderreactionstobemappedbycomputationwithincreasingaccuracyandthepropertiesoftransitionstatesandinaccessiblemoleculestobestudied.Evenalimitednumberofsolventmoleculesmaybeincludedinthecomputationswhich,whateverthcprecision,hasgreatlyenhancedunderstandingandincreasedconfidenceinresultsinferredfromexperimentalmeasurements.Singleelectrontransferrouteshaverevealedunexpectedaspectsofwhatwereconsideredwell-understoodreactionssuchasnitration.LinearFreeEnergyRelationships,increasinginsophistication,continuetocontributepowerfullytoreactivitytheoryandtheexperimentalmeasurementofelectronictransmission.Thetheoryandpractiseofchiralinductionhascomeunderincreasingscrutinyfollowingtheeconomicimportanceofasymmetricsynthesiswhiletheinvolvementofmetalsinorganicchemistryhasreachedthepointwhichmakesorganometallicchemistryasubjectofasizeandcomplexitytowarrantseparatetreatmentandtoogreattobeincludedwithinabookofthissize.