Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In ...Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In contrast to the well-developed functionalization of one carbon fragment after C–C bond cleavage,herein,we report a novel electro-reductive carboxylation of C(sp^(3))–C(sp^(3))bond in multi-aryl ethanes with carbon dioxide(CO_(2))by utilizing both carbon fragments.Thus,this reaction exhibits an atom-,step-economic approach for the synthesis of carboxylic acids,fulfilling principal aspirations of organic synthesis.Moreover,this method features mild reaction conditions,broad substrate scope,and good functional group tolerance.Symmetric and asymmetric substrates bearing primary,secondary,or tertiary C(sp^(3))–C(sp^(3))bonds are all amenable to this strategy,enabling one or two structurally different carboxylic acids to be facilely constructed at the same time.Mechanistic investigations indicate that carbanions might be the key intermediates in this reaction,which could be captured by CO_(2)efficiently.展开更多
Opaque polyploid cells capable of forming megamitochondria are a constant <span style="font-family:Verdana;">feature in colonies of Ishikawa endometrial epithelia, accounting for ap</span><spa...Opaque polyploid cells capable of forming megamitochondria are a constant <span style="font-family:Verdana;">feature in colonies of Ishikawa endometrial epithelia, accounting for ap</span><span style="font-family:Verdana;">proximately 5</span><span style="font-family:Verdana;">% </span><span style="font-family:Verdana;">-</span><span style="font-family:;" "=""> </span><span style="font-family:;" "=""><span style="font-family:Verdana;">10% of the cells. Opaque cells appear to communicate with other </span><span style="font-family:Verdana;">opaque cells via membrane extensions and with other cells in a colony by </span><span style="font-family:Verdana;">extra</span></span><span style="font-family:Verdana;">-</span><span style="font-family:;" "=""><span style="font-family:Verdana;">cellular vesicles. Opaque cells form first as rectangular structures, somewhat larger than surrounding monolayer cells. The cells eventually round up, re</span><span style="font-family:Verdana;">maining in the colony for 20 or more hours before detaching. The most </span><span style="font-family:Verdana;">un</span><span style="font-family:Verdana;">usual characteristic of Ishikawa opaque cells is their capacity to form mitonucleons, megamitochondria that surround aggregated chromatin. This</span><span style="font-family:Verdana;"> paper reviews evidence that adaptations resulting in megamitochondria i</span><span style="font-family:Verdana;">nclude a loss of the capacity for oxidative phosphorylation leaving the adapted </span><span style="font-family:Verdana;">megamitochondria reliant on metabolism such as reductive carboxylation.</span></span>展开更多
A highly efficient and facile protocol for the selective reduction of carboxylic acid of Fenofibric acid to corresponding alcohol was developed. The selective reduction was carried out by activation of carboxylic acid...A highly efficient and facile protocol for the selective reduction of carboxylic acid of Fenofibric acid to corresponding alcohol was developed. The selective reduction was carried out by activation of carboxylic acid by mixed anhydride followed by the reaction of sodium borohydride in presence of methanol. This is the first example of chemoselective reduction of carboxylic acid to alcohol in presence of a ketone without any external catalyst or ligand in a single step. The reaction offers wide applicability for the selective carboxylic group reduction methodology. The chemoselective reduction was demonstrated by the reduction of Fenofibric acid, an active metabolite of the drug Fenofibrate, to corresponding alcohol in excellent selectivity, yield, and purity.展开更多
Enantiomerically pure syn-4,5-dihydroxy carboxylic acid lactones were prepared by microbial reduction of acyl lactones with resting cell of Aspergillus niger.
基金supported by the National Natural Science Foundation of China(22225106,22201027)the Fundamental Research Funds for the Central Universities。
文摘Despite the recent advances in the selective functionalization of C–C bonds in specific substrates,cleavage and functionalization of C–C bonds in acyclic substrates,such as ethane derivatives,remains challenging.In contrast to the well-developed functionalization of one carbon fragment after C–C bond cleavage,herein,we report a novel electro-reductive carboxylation of C(sp^(3))–C(sp^(3))bond in multi-aryl ethanes with carbon dioxide(CO_(2))by utilizing both carbon fragments.Thus,this reaction exhibits an atom-,step-economic approach for the synthesis of carboxylic acids,fulfilling principal aspirations of organic synthesis.Moreover,this method features mild reaction conditions,broad substrate scope,and good functional group tolerance.Symmetric and asymmetric substrates bearing primary,secondary,or tertiary C(sp^(3))–C(sp^(3))bonds are all amenable to this strategy,enabling one or two structurally different carboxylic acids to be facilely constructed at the same time.Mechanistic investigations indicate that carbanions might be the key intermediates in this reaction,which could be captured by CO_(2)efficiently.
文摘Opaque polyploid cells capable of forming megamitochondria are a constant <span style="font-family:Verdana;">feature in colonies of Ishikawa endometrial epithelia, accounting for ap</span><span style="font-family:Verdana;">proximately 5</span><span style="font-family:Verdana;">% </span><span style="font-family:Verdana;">-</span><span style="font-family:;" "=""> </span><span style="font-family:;" "=""><span style="font-family:Verdana;">10% of the cells. Opaque cells appear to communicate with other </span><span style="font-family:Verdana;">opaque cells via membrane extensions and with other cells in a colony by </span><span style="font-family:Verdana;">extra</span></span><span style="font-family:Verdana;">-</span><span style="font-family:;" "=""><span style="font-family:Verdana;">cellular vesicles. Opaque cells form first as rectangular structures, somewhat larger than surrounding monolayer cells. The cells eventually round up, re</span><span style="font-family:Verdana;">maining in the colony for 20 or more hours before detaching. The most </span><span style="font-family:Verdana;">un</span><span style="font-family:Verdana;">usual characteristic of Ishikawa opaque cells is their capacity to form mitonucleons, megamitochondria that surround aggregated chromatin. This</span><span style="font-family:Verdana;"> paper reviews evidence that adaptations resulting in megamitochondria i</span><span style="font-family:Verdana;">nclude a loss of the capacity for oxidative phosphorylation leaving the adapted </span><span style="font-family:Verdana;">megamitochondria reliant on metabolism such as reductive carboxylation.</span></span>
文摘A highly efficient and facile protocol for the selective reduction of carboxylic acid of Fenofibric acid to corresponding alcohol was developed. The selective reduction was carried out by activation of carboxylic acid by mixed anhydride followed by the reaction of sodium borohydride in presence of methanol. This is the first example of chemoselective reduction of carboxylic acid to alcohol in presence of a ketone without any external catalyst or ligand in a single step. The reaction offers wide applicability for the selective carboxylic group reduction methodology. The chemoselective reduction was demonstrated by the reduction of Fenofibric acid, an active metabolite of the drug Fenofibrate, to corresponding alcohol in excellent selectivity, yield, and purity.
文摘Enantiomerically pure syn-4,5-dihydroxy carboxylic acid lactones were prepared by microbial reduction of acyl lactones with resting cell of Aspergillus niger.