103615-36-7Relevant articles and documents
Toward a Large-Scale Approach to Milnacipran Analogues Using Diazo Compounds in Flow Chemistry
Müller, Simon T. R.,Murat, Aurélien,Hellier, Paul,Wirth, Thomas
, p. 495 - 502 (2016)
The safe use of diazo reagents for the preparation of a key structure in the synthesis of milnacipran analogues is described herein. Using continuous flow technology, the diazo reagent is synthesized, purified, dried, and subsequently used in semi-batch mode for an intramolecular cyclopropanation. Side products formed in the reaction are isolated and rationalized to optimize the process. Different separation techniques in flow are compared with regard to their ability to produce pure and dry diazo reagents. The studies yield a scalable process to a key intermediate in the syntheses of milnacipran and its possible substituted analogues.
Dirhodium(II)/Xantphos-Catalyzed Relay Carbene Insertion and Allylic Alkylation Process: Reaction Development and Mechanistic Insights
Liang, Xinyi,Lu, Bin,Peng, Qian,Wang, Xiaoming,Wang, Zijian,Zhang, Jinyu
supporting information, p. 11799 - 11810 (2021/08/16)
Although dirhodium-catalyzed multicomponent reactions of diazo compounds, nucleophiles and electrophiles have achieved great advance in organic synthesis, the introduction of allylic moiety as the third component via allylic metal intermediate remains a formidable challenge in this area. Herein, an attractive three-component reaction of readily accessible amines, diazo compounds, and allylic compounds enabled by a novel dirhodium(II)/Xantphos catalysis is disclosed, affording various architecturally complex and functionally diverse α-quaternary α-amino acid derivatives in good yields with high atom and step economy. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium(II)-catalyzed carbene insertion and allylic alkylation process, in which the catalytic properties of dirhodium are effectively modified by the coordination with Xantphos, leading to good activity in the catalytic allylic alkylation process.
A chiral cobalt(II) complex catalyzed asymmetric formal [3+2] cycloaddition for the synthesis of 1,2,4-triazolines
Ma, Baiwei,Luo, Weiwei,Lin, Lili,Liu, Xiaohua,Feng, Xiaoming
, p. 4077 - 4079 (2017/04/13)
A highly efficient catalytic asymmetric formal [3+2] cycloaddition reaction of 5-alkoxyoxazoles with azodicarboxylate compounds has been realized by a chiral N,N′-dioxide/Co(BF4)2·6H2O complex. A series of poly-substituted 1,2,4-triazolines compounds were obtained in moderate to excellent yields (70-99%) with excellent enantioselectivities (82-98% ee).
Expeditious microwave-assisted synthesis of 5-alkoxyoxazoles from α-triflyloxy esters and nitriles
Jouanno, Laurie-Anne,Sabot, Cyrille,Renard, Pierre-Yves
, p. 8549 - 8555 (2012/11/07)
A rapid and general access to diversely substituted 5-alkoxyoxazoles 2 (i.e., R1, R2 = alkyl, phenyl) from easily accessible α-triflyloxy/hydroxy esters 1 and nitriles with good yields (41-76%) is reported. The versatility of the cyc
Preparation of substituted oxazoles by ritter reactions of α-oxo tosylates
Lai, Ping-Shan,Taylor, Mark S.
experimental part, p. 1449 - 1452 (2010/09/14)
The Lewis acid catalyzed Ritter reaction of α-oxo tosylates with nitriles forms the basis of an efficient synthesis of oxazoles. Oxazoles with various substituents can be readily prepared from inexpensive starting materials. Georg Thieme Verlag Stuttgart.
MODIFICATION OF SINGLET CARBENE REACTIVITIES BY SOLVENT
Tomoika, H.,Ozaki, Y.,Izawa, Y
, p. 4987 - 4994 (2007/10/02)
The solvent effect on the reactivity of singlet carbenes has been investigated.Competition reactions between pairs of alcohols for arylcarbenes in various solvents indicates that the O-H insertion selectivity is influenced only by 1,4-dioxane.Thus, phenylcarbene is some 33 times more reactive toward methanol relative to t-butyl alcohol in 90 molpercent dioxane than without solvent.Similar competition reactions between alcohol and olefin indicate that the O-H insertion-addition selectivities of arylcarbenes are considerably altered by dioxane.These results are interpreted as indicating that dioxane stabilizes singlet carbenes by complexing with its ione pairs of electrons.
