Radicals in Synthesis I

213 Pages·2006·4.87 MB·English

by  David Crich

263
Topics in Current Chemistry
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Radicals in Synthesis I
MethodsandMechanisms
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Preface
“I didn’t think that radical chemistry could be so mild and selective,” is the
nicer version of comments one often hears after seminars. What is the un-
derlyingreasonforthemisconception?Probablythatradicaltransformations
oftenseemcounterintuitive tothosebroughtupwithclassicalretrosynthetic
schemes. As a result, the use of radicals is considered by many synthetic
chemists as a last resort only to be used when other more traditionalmeth-
odshave failed. Additionally, radicalreactions are usually regarded asbeing
unselectiveandinvolvingtoxicreagents.
This is, of course, false; such a conservative approach neglects the mild,
selective,andoriginalsolutionsavailablethroughusingradicalchemistryfor
demandingsyntheticproblems.Moreover,asolidphysicalorganicunderstand-
ingofthemechanismbehindmostradicalreactionshasnowbeenestablished.
This basis serves us well in predicting many results as well as in developing
novelreactions.Inshort,radicalchemistryhasdevelopedwithamazingspeed
fromalaboratorycuriosityintoanintegral,predictable,andhighlyproductive
partoforganicchemistry.Thisaccountismeant tofurtherspreadthispoint
ofview.
The first volume (Methods and Mechanisms) concentrates on the mecha-
nistic aspects of radical chemistry and the development of novel methods,
while thesecond volume (Complex Molecules) focuses onthe use ofradicals
in synthetic applications. While such traditional separation (novel methods
are increasingly aimed at preparing complex molecules and the synthesis of
complex molecules requires careful planning) may seem a little outdated at
thebeginning ofthe21st century, itisnevertheless employed forthesake of
convenience.
The chapters, written by leading experts, provide state-of-the-art reviews
ofexcitingandpertinenttopicsofcurrentresearchinradicalchemistry.These
includeadiscussionofcomputeddataconcerningradicalstabilitiesandtheir
evaluation,thesurprisingchemistryofradicalcations,modernconceptsand
reagents for enantioselective radical chemistry, the mechanistic aspects of
epoxideopeningviaelectrontransfer,theevolutionofecologicallybenignand
efficient tin-free radical reactions, the attractive novel reagents and radical
traps for unusual cyclizations, the exciting possibilities of xanthate derived
radical processes, the emerging field of radical chemistry on solid supports,
X Preface
therecentdevelopmentofhighlyversatileradicaltandemreactions,themild
and selective derivatization of amino acids and sugars through the use of
radicals, and the increasing use of Cp TiCl-catalyzed and -mediated radical
2
reactionsinnaturalproductsynthesis.
Of coursenotalloftheexciting recent developments inradicalchemistry
canbecovered indepth in just twobooks.It isthereforeplanned toexpand
thisseriesinthenearfuture. Ioffermyapologiestotheauthorsleftoutthis
timeandaskthemtocontributenexttime!
Hopefullythisbookwillmeetthechallengeofconvincingalargenumberof
scientistsofthebenefitsofradicalchemistryandsparknoveldevelopmentsin
thefieldsofnewradicalmethodologyandtheapplicationofradicalreactions
inthesynthesisofcomplexmolecules.
Bonn,February2006 AndreasGansäuer