转自：康龙化成夜夜撸改成什么

RingContractionofSaturatedCyclicAminesandRearrangementofAcyclicAminesThroughTheirCorrespondingHydroxylamines

YiPeng[a]，GuoqiangWang[b]，*HendrikF.T.Klare[a]，andMartinOestreich[a]*

[a]InstitutfürChemie，TechnischeUniversitätBerlin，Strassedes17.Juni115，10623Berlin(Germany);

[b]InstituteofTheoreticalandComputationalChemistry，SchoolofChemistryandChemicalEngineering，NanjingUniversity，Nanjing，210023，P.R.China

—Angew.Chem.Int.Ed.，2024，63，e202410483

RecommendedbyRuiJin_MC5

KEYWORDS:skeletalediting(反馈类型)，ringcontraction(反馈类型)，rearrangement(反馈类型)，C(sp3)–N(成键类型)，B(C6F5)3(催化剂)，hydrosilane(试剂)，hydroxylamine(原料)，amine(居品)，scaffoldhopping(其他)，targetedcarbonatomdeletion(其他)

ABSTRACT:Comparedtomodificationsatthemolecularperiphery，skeletaladjustmentspresentgreaterchallenges.Withinthiscontext，skeletalrearrangementtechnologystandsoutforitssignificantadvantagesinrapidlyachievingstructuraldiversity.Yet，thedevelopmentofthistechnologyforringcontractionofsaturatedcyclicaminesremainsexceedinglyrare.Whilemostexistingmethodsrelyonspecificsubstitutionpatternstoachieveringcontraction，thereisapersistentdemandforamoregeneralstrategyforsubstitution-freecyclicamines.Toaddressthisissue，wereportaB(C6F5)3-catalyzedskeletalrearrangementofhydroxylamineswithhydrosilanes.Thismethodology，whencombinedwiththeN-hydroxylationofamines，enablestheregioselectiveringcontractionofcyclicaminesandprovesequallyeffectiveforrapidreorganizationofacyclicamineskeletons.Bythis，thedirectscaffoldhoppingofdrugmoleculesandthestrategicdeletionofcarbonatomsareachievedinamildmanner.Basedonmechanisticexperimentsanddensityfunctionaltheorycalculations，apossiblemechanismforthisprocessisproposed.

Reactiondesignanddevelopment

Optimizationofthereactionconditions

Scopeofsaturatedcyclicaminesintheringcontractionandapplicationsofthering-contractionstrategy

Scopeofacyclicsubstratesinskeletalreorganization

Reactionpathwaysfortheringcontractionofhydroxylamine1awithMePhSiH2

SummaryandComments

Insummary，OestreichandWangetal.havedevelopedaB(C6F5)3-catalyzedskeletalrearrangementofhydroxylamineswithhydrosilanes，overcomingthelimitationsofthetraditionaluncatalyzedStieglitzrearrangement.Thisadvancement，whenintegratedwithefficientN-hydroxylationtechniquesforamines，enablestherapidreorganizationofamineskeletons，particularlyshowcasinghighlyregioselectiveringcontractionofcyclicamines.Incontrasttopreviousmethodsthatrequiredspecificsubstitutionpatternsonthering，ourrearrangementstrategydemonstratesenhancedflexibility，accommodatingawidearrayofcyclicamines.Thepotentialofourstrategyforscaffoldhoppingandtargetedcarbonatomdeletionhasbeensubstantiated.DFTcalculationsshowthattheoverallreactionisanexergonicprocess.Althoughtwopotentialpathwaysfortheringopeningoftheimplicatedphenoniumionarekineticallyviable，thebarrierlesshydridetransferfromtheborohydridetothemethylenegroupwithinthephenoniumionappearstobethepreferredpathway，comparedtothedirectringopeningofthephenoniumionwithahigherenergybarrier.

柏林工业大学MartinOestreich与南京大学GuoqiangWand课题组共同报说念了一类羟胺在B(C6F5)3催化以及MePhSiH2的作用下发生的分子骨架重排反馈。该反馈克服了传统Stieglitz重排的底物局限性，通过富足胺分子的骨架快速重组，完了了环状胺的高度区域选拔性缩环反馈。

（转自：康龙化成）夜夜撸改成什么