A highly efficient and enantioselective method for the asymmetric reductive amination ofβ-keto phosphine de-rivatives was disclosed,and the correspondingβ-amino phosphine oxides could be obtained in high yields(up t...A highly efficient and enantioselective method for the asymmetric reductive amination ofβ-keto phosphine de-rivatives was disclosed,and the correspondingβ-amino phosphine oxides could be obtained in high yields(up to 97%yield)and excellent enantioselectivities(up to 97%ee).Moreover,the reaction worked well on a gram scale,indicating that our protocol has potential applications in the synthesis of chiral ligands and organocatalysts.展开更多
Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemi...Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemical industry.In this paper,a dual metal catalysis system combining a Ru-isomerization catalyst and a Rh-linear-hydroformylation catalyst satisfying the“4S”criterions was reported for isomerization-linear-hydroformylation of C4 raffinate(mixed butenes)and internal olefins.The optimized dual metal catalyst system hydroformylated Raffinate II feed to valuable valeraldehyde in 98%linear selectivity(n:i=49),80%conversion and high activity of 1069 h^(−1)TOF whereas 96%linear selectivity(n:i=24),71%conversion and 948 h^(−1)TOF were observed using only the Rh-hydroformylation catalyst.Notably,valeraldehyde are produced in million tons scale annually for making non-toxic plasticizer DPHP.Various 2-olefins were also converted to linear aldehydes in>98%linear selectivity(n:i>49),78%-82%conversion and high activity of 802-851 h^(−1)TOF.展开更多
基金the National Natural Science Foundation of China(No.21901107)Shenzhen Bay Laboratory(No.SZBL2019062801006)+5 种基金Shenzhen Science and Technology Innovation Committee(No.KQTD20150717103157174)Key-Area Research and Development Program of Guangdong Province(No.2020B010188001)Stable Support Plan Program of Shenzhen Science and Technology Innovation Committee(No.20200925161222002)Innovative Team of Universities in Guangdong Province(No.2020KCXTD016).G.Q.Chen gratefully acknowledges the National Natural Science Foundation of China(Nos.21901107 and 22171129)the Guangdong Basic and Applied Basic Research Foundation(No.2022B1515020055)the Shenzhen Science and Technology Innovation Committee(No.JCYJ20210324104202007)for financial support.B.Ma is indebted to the financial support from the National Natural Science Foundation of China(No.22001113)B.Ma is the National Natural Science Foundation of China(No.22001113).
文摘A highly efficient and enantioselective method for the asymmetric reductive amination ofβ-keto phosphine de-rivatives was disclosed,and the correspondingβ-amino phosphine oxides could be obtained in high yields(up to 97%yield)and excellent enantioselectivities(up to 97%ee).Moreover,the reaction worked well on a gram scale,indicating that our protocol has potential applications in the synthesis of chiral ligands and organocatalysts.
基金R.Zhang gratefully acknowledges the Free Exploration Fund from the Science and Technology Innovation Committee of Shenzhen(No.JCYJ20170817104824122)We are grateful for the financial support from the National Natural Science Foundation of China(No.22001113)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Isomerization-linear-hydroformylation is demanding,however,not an addressed issue,for the production of value-added linear aldehydes by converting cheap and abundant internal alkenes available from bio-&petrochemical industry.In this paper,a dual metal catalysis system combining a Ru-isomerization catalyst and a Rh-linear-hydroformylation catalyst satisfying the“4S”criterions was reported for isomerization-linear-hydroformylation of C4 raffinate(mixed butenes)and internal olefins.The optimized dual metal catalyst system hydroformylated Raffinate II feed to valuable valeraldehyde in 98%linear selectivity(n:i=49),80%conversion and high activity of 1069 h^(−1)TOF whereas 96%linear selectivity(n:i=24),71%conversion and 948 h^(−1)TOF were observed using only the Rh-hydroformylation catalyst.Notably,valeraldehyde are produced in million tons scale annually for making non-toxic plasticizer DPHP.Various 2-olefins were also converted to linear aldehydes in>98%linear selectivity(n:i>49),78%-82%conversion and high activity of 802-851 h^(−1)TOF.
