Study Of Addition Reaction And Coupling Reaction Of P-H/P-OH Bonds

Organophosphorus compounds have a wide range of applications.With the increasing importance of organophosphorus compounds in pesticides,pharmaceuticals,and functional materials,designing a new and efficient method for constructing P-C/P-X bonds has become a leading task in organic synthesis chemistry.There are several methods for preparing organophosphorus compounds,such as the Atherton-Todd reaction,but these reagents have the disadvantages of being sensitive to water/air and having poor tolerance to functional groups,which limits the using.Arbuzov reaction is mainly used to synthesize alkyl phosphorus compounds,so this method is also greatly limited.Existing methods usually require expensive transition metals and harsh reaction conditions,such as Pd-catalyzed Arbuzov or Hirao reactions.In addition to the conventional nucleophilic substitution methods,the most direct method for preparing such compounds are the coupling reactions between the P?O?-H/P?O?-X compound with the nucleophiles,unfortunately,the reagents used are either expensive or sensitive to moisture/air and difficult to transport and store.Therefore,the best method is to use P-H/P?O?-OH compounds that are cheap and readily available and are stable to air to selectively construct the corresponding P-C bonds or P-X bonds.This thesis mainly includes the following:?1?Base catalyzed allylic-and 1,6-substitution of quinone monoketals with P?O?-H compounds;?2?Transition metal catalyzed cross-coupling reaction of P?O?-OH compounds with cyclic diaryliodonium salts;?3?Bu₄NI-catalyzed dehydrogenative coupling of diaryl phosphinic acids with C?sp³?-H bonds of arenes.In this paper,we also explored of the reaction mechanisms.The mechanisms are described in detail through mechanism control experiments,free radical capture experiments,and nuclear magnetic resonance detection.