Organocatalytic 1,4-Addition Reaction of 2-Formyl(thio)esters to Vinylketones: An Efficient Access to Acyclic Chiral Building Blocks with a Quaternary Carbon Stereocenter

2015 ◽  
Vol 21 (52) ◽  
pp. 18971-18974 ◽  
Author(s):  
Toshifumi Tatsumi ◽  
Tomonori Misaki ◽  
Takashi Sugimura
Keyword(s):  
Addition Reaction ◽  
Building Blocks ◽  
Quaternary Carbon ◽  
Efficient Access

Electrochemical Oxidative Esterification of Thiophenols: Efficient Access to Sulfinic Esters

2020 ◽  
Vol 17 (7) ◽  
pp. 540-547
Author(s):  
Chun-Hui Yang ◽  
Cheng Wu ◽  
Jun-Ming Zhang ◽  
Xiang-Zhang Tao ◽  
Jun Xu ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Efficient Method ◽  
High Efficiency ◽  
Building Blocks ◽  
Constant Current ◽  
Good Efficiency ◽  
Oxidative Esterification ◽  
Efficient Access ◽  
New Applications ◽  
Sulfinic Esters

Background: The sulfinic esters are important and useful building blocks in organic synthesis. Objective: The aim of this study was to develop a simple and efficient method for the synthesis of sulfinic esters. Materials and Methods: Constant current electrolysis from thiols and alcohols was selected as the method for the synthesis of sulfinic esters. Results and Discussion: A novel electrochemical method for the synthesis of sulfinic esters from thiophenols and alcohols has been developed. Up to 27 examples of sulfinic esters have been synthesized using the current methods. This protocol shows good functional group tolerance as well as high efficiency. In addition, this protocol can be easily scaled up with good efficiency. Notably, heterocycle-containing substrates, including pyridine, thiophene, and benzothiazole, gave the desired products in good yields. A plausible reaction mechanism is proposed. Conclusion: This research not only provides a green and efficient method for the synthesis of sulfinic esters but also shows new applications of electrochemistry in organic synthesis. It is considered that this green and efficient synthetic protocol used to prepare sulfinic esters will have good applications in the future.

Kinetic resolution of oxime esters with lipases — synthesis of enantiomerically enriched building blocks with quaternary carbon centers and formal total synthesis of perhydro histrionicotoxin

2002 ◽  
Vol 80 (6) ◽  
pp. 686-691 ◽  
Author(s):  
Nicole Diedrichs ◽  
Ralf Krelaus ◽  
Ina Gedrath ◽  
Bernhard Westermann
Keyword(s):  
Substrate Specificity ◽  
Total Synthesis ◽  
Solvent Effects ◽  
Kinetic Resolution ◽  
Building Blocks ◽  
Beckmann Rearrangement ◽  
Optically Active ◽  
Quaternary Carbon ◽  
Carbon Centers

Enantiomerically enriched oximes bearing stereogenic quaternary carbon centers can be obtained by lipase-catalyzed kinetic resolution of oxime esters. Substrate specificity, solvent effects, and the use of different lipases are discussed. Kinetic resolution of butyrylated oximes by lipase PS in the presence of n-butanol gave the best ee-values of both the saponified oxime and the residual oxime ester. Subsequent stereospecific Beckmann rearrangement of an enantiomerically enriched oxime provided lactams, which could be employed for the synthesis of optically active perhydro histrionicotoxin.Key words: oxime, lipase, kinetic resolution, Beckmann rearrangement, perhydro histrionicotoxin.

Construction of unique SCF3-containing building blocks via allylic alkylation of Morita–Baylis–Hillman adducts

2020 ◽  
Vol 18 (11) ◽  
pp. 2085-2093
Author(s):  
Priyanka Halder ◽  
Mahesh D. Pol ◽  
Milind M. Ahire ◽  
Santosh B. Mhaske
Keyword(s):  
Building Blocks ◽  
Lewis Base ◽  
Allylic Alkylation ◽  
Efficient Access

Lewis base-catalyzed allylic alkylation of MBH adducts with α-SCF3 ketones has been demonstrated to provide an efficient access to a series of highly functionalized scaffolds featuring trifluoromethanesulfinyl motif on a stereogenic carbon.

scholarly journals Metal-Catalyzed Oxidative Coupling of Ketones and Ketone Enolates

Synthesis ◽  
2018 ◽  
Vol 50 (11) ◽  
pp. 2150-2162 ◽  
Author(s):  
Sandip Murarka ◽  
Andrey Antonchick
Keyword(s):  
Oxidative Coupling ◽  
Cross Coupling ◽  
Building Blocks ◽  
Dicarbonyl Compounds ◽  
Carbocyclic Compounds ◽  
Efficient Access ◽  
Ketone Enolates ◽  
Metal Catalyzed

Recent years have witnessed a significant advancement in the field of radical oxidative coupling of ketones towards the synthesis of highly useful synthetic building blocks, such as 1,4-dicarbonyl compounds, and biologically important heterocyclic and carbocyclic compounds. Besides oxidative homo- and cross-coupling of enolates, other powerful methods involving direct C(sp3)–H functionalizations of ketones­ have emerged towards the synthesis of 1,4-dicarbonyl compounds. Moreover, direct α-C–H functionalization of ketones has also allowed an efficient access to carbocycles and heterocycles. This review summarizes all these developments made since 2008 in the field of metal-catalyzed/promoted radical-mediated functionalization of ketones at the α-position.1 Introduction2 Synthesis of 1,4-Dicarbonyl Compounds3 Synthesis of Heterocyclic Scaffolds4 Synthesis of Carbocyclic Scaffolds5 Conclusion

Doyle-Kirmse Reaction Using 3,3-Difluoroallyl Sulfide and N-Sulfonyl-1,2,3-triazole: An Efficient Access to gem-Difluoroallylated Multifunctional Quaternary Carbon

2021 ◽  
Author(s):  
Jiazhuang Wang ◽  
Jingwen Yu ◽  
Junyu Chen ◽  
Yubo Jiang ◽  
Tiebo Xiao
Keyword(s):  
Sigmatropic Rearrangement ◽  
Quaternary Carbon ◽  
Quaternary Center ◽  
Efficient Access

Doyle-Kirmse reaction of N-sulfonyl-1,2,3-triazole with 3,3-difluoroallyl sulfide through Rh(II)-catalyzed [2,3]-sigmatropic rearrangement has been developed, which affords an efficient access to multifunctional quaternary center containing aryl, imino, thio, and brominated gem-difluoroallyl....

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