Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable...Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable benzylation reagents.At present,the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands.It is necessary to develop novel and practical methods for their preparation.In this work,a novel copper‐catalyzed deoxygenative gem‐hydroborylation of aromatic aldehydes and ketones has been developed.This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates,in which broad functional group tolerance was presented.Widely available B2pin2(pin=pinacol)was used as the boron source and alcoholic proton was applied as the hydride source.展开更多
The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.H...The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.展开更多
文摘Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable benzylation reagents.At present,the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands.It is necessary to develop novel and practical methods for their preparation.In this work,a novel copper‐catalyzed deoxygenative gem‐hydroborylation of aromatic aldehydes and ketones has been developed.This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates,in which broad functional group tolerance was presented.Widely available B2pin2(pin=pinacol)was used as the boron source and alcoholic proton was applied as the hydride source.
基金financially supported by the National Natural Science Foundation of China(Nos.92061110,21925303,21829501,21771186,21222301,21528303,and 21171170)the Anhui Provincial Natural Science Foundation(2108085Y05 and 2108085MB56)+1 种基金Collaborative Innovation Program of Hefei Science Center,CAS(Nos.2020HSCCIP005 and 2022HSC-CIP018)the Hefei National Laboratory for Physical Sciences at the Microscale(KF2020102).
文摘The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.
