Study On B-H Insertion And C-H Activation Cyclization Of Sulfoxonium Ylide

Sulfoxonium ylides are zwitterionic compounds characterised by a carbanion flanked by a positively charged sulfur atom.The carbanion has strong nucleophilicity and can coordinate with metal to release a molecule of DMSO and generate highly active metal carbene intermediate.Similar to diazo compounds in chemical properties,sulfoxonium ylides are widely used in X-H insertion,C-H activation,cycloaddition,cross coupling and other reactions.Herein,X-H insertion and C-H activation involving sulfoxonium ylides in recent years were summarized in detail,and α-boryl carbonyls,dihydropyrimidoindolone and tricyclic [1,3]oxazino[3,4-a]indol-1-ones derivatives were rapidly and efficiently synthesized from stable sulfoxonium ylides.The specific content is divided into the following three parts.In chapter 1,the application of sulfoxonium ylides in drug synthesis was briefly introduced,and X-H insertion and C-H activation involving sulfoxonium ylides were introduced in detail.In chapter 2,the research significance and synthesis methods of α-boryl carbonyls are introduced.Then,the synthesis of α-boryl carbonyls by B-H insertion of sulfoxonium ylides and trimethylamine-borane under iridium catalysis was developed.This synthetic method has the characteristics of broad substrate scope and high compatibility of functional groups.Meanwhile,the reaction can also be used for the late-stage modification of complex drug molecules,such as naproxen,probenecid,ibuprofen,oxaprozin,isoxepac,estrone and testosterone.In chapter 3,the research value of polycyclic indole compounds and the methods of synthesizing these compounds are introduced.Subsequently,we report the example of cascade Rh(III)-catalyzed C-H activation/intramolecular chemodivergent annulation reaction between N-carbamoylindoles and sulfoxonium ylides,which provide the synthesis of dihydropyrimido-indolone and tricyclic [1,3]oxazino[3,4-a]indol-1-ones derivatives.This method shows a feature of mild and redox neutral reaction conditions,broad substrate scope and excellent functional-group compatibility.Meanwhile,the reaction can also be used for the late-stage modification of ibuprofen,probenecid and testosterone.