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.

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.

scholarly journals π-Conjugated Heteroles Containing Group 13 Elements

2021 ◽  
Author(s):  
Sossina Gezahegn
Keyword(s):  
Energy Gap ◽  
Theoretical Calculations ◽  
Building Blocks ◽  
Lewis Base ◽  
Group 13 ◽  
Conjugated Systems ◽  
Energy Gaps ◽  
Potential Formation ◽  
Lewis Adduct ◽  
Homo Lumo

This research targeted the synthesis of group 13 neutral heteroles via transmetallation of the tin atom in stannole moieties. The synthesis of Heteroles of 15a (1-chloro-2,3,4,5-tetraphenylborole), 15b (1-chloro-2,3,4,5-tetraphenylaluminole) and 15c (1-chloro-2,3,4,5-tetraphenylgallole) were attempted. The potential formation of Lewis base adducts were explored through the addition of a coordinating solvent of THF, Et3N, and Et2O and characterized with NMR (1H, 13C and 11B where applicable). It was attempted to synthesize Polymer 17a from the di-brominated borole monomer 16a via a Pd-catalyzed polycondensation reaction. THF was subsequently added to the polymer in an attempt to produce the polymer adduct 17a·THF. This was performed to produce a stable enough material for GPC analysis. The polymer was also characterized with NMR. Theoretical calculations were undertaken at the B3LYP/6-31G* level of DFT to help identify the effect of HOMO-LUMO energy gap of the above heteroles and their adducts. DFT calculations reveal that monomers and oligomer energy gaps can be tuned by substituents attached to the heterole, the type of Lewis adduct formed and the degree of catenation. These monomers and oligomers could potentially be novel building blocks for the synthesis of small energy gap π-conjugated systems.

Synthesis of Optically Active Bifunctional Building Blocks through Enantioselective Copper-Catalyzed Allylic Alkylation Using Grignard Reagents

2007 ◽  
Vol 72 (7) ◽  
pp. 2558-2563 ◽  
Author(s):  
Anthoni W. van Zijl ◽  
Fernando López ◽  
Adriaan J. Minnaard ◽  
Ben L. Feringa
Keyword(s):  
Building Blocks ◽  
Optically Active ◽  
Grignard Reagents ◽  
Allylic Alkylation

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

Copper/Lewis base cooperatively catalyzed asymmetric allylic alkylation of Morita−Baylis−Hillman carbonates with azomethine ylides

2021 ◽  
Author(s):  
Yimin Hu ◽  
Zhengyang Yan ◽  
Wangyu Shi ◽  
Jianning Liao ◽  
Min Liu ◽  
...  
Keyword(s):  
Lewis Base ◽  
Azomethine Ylides ◽  
Allylic Alkylation ◽  
Asymmetric Allylic Alkylation ◽  
Cooperative Catalysis

In this paper, an asymmetric allylic alkylation of easily available azomethine ylides with Morita−Baylis−Hillman (MBH) Carbonates through a copper (I) / Lewis base cooperative catalysis strategy has been realized. The...

Unconventional Transformations of Morita–Baylis–Hillman Adducts

Synthesis ◽  
2020 ◽  
Author(s):  
Xavier Companyó ◽  
Alessio Calcatelli ◽  
Alessio Cherubini-Celli ◽  
Edoardo Carletti
Keyword(s):  
Transition Metal Complexes ◽  
Short Review ◽  
Lewis Base ◽  
Base Catalysis ◽  
Allylic Alkylation ◽  
One Pot ◽  
Allylic Alkylations ◽  
Cascade Processes ◽  
Dual Activation ◽  
Trisubstituted Alkenes

Morita–Baylis–Hillman (MBH) adducts are versatile starting materials widely employed in Lewis base catalysis. A myriad of different transformations have been reported based on either allylic alkylations with stabilised nucleophiles or annulations with diverse dipolarophiles. Apart from these two conventional types of reactivity, MBH adducts have recently been implemented in alternative and complementary catalytic strategies, including: (i) one-pot and cascade transformations, where additional chemical bonds are formed following the asymmetric allylic alkylation event in a single synthetic operation; (ii) regioselective α-allylations for the synthesis of trisubstituted alkenes; and (iii) dual activation strategies, involving Lewis base catalysis together with transition metal complexes or light, enabling allylic alkylations with nonstabilised nucleophiles and cascade processes. The present Short Review summarises the most significant unconventional catalytic transformations of racemic MBH adducts reported within the last decade.1 Introduction2 Multi-Step Single-Vessel Transformations (path iii)2.1 One-Pot Transformations2.2 Cascade Transformations3 α-Allylations (path iv)3.1 SN2′ Mechanism3.2 SN2′–SN2 Mechanism3.3 Miscellaneous Mechanisms4 Dual Activation (path v)4.1 MBH Adduct as Electrophile4.2 MBH Adduct as Nucleophile5 Summary and Outlook

scholarly journals π-Conjugated Heteroles Containing Group 13 Elements

2021 ◽  
Author(s):  
Sossina Gezahegn
Keyword(s):  
Energy Gap ◽  
Theoretical Calculations ◽  
Building Blocks ◽  
Lewis Base ◽  
Group 13 ◽  
Conjugated Systems ◽  
Energy Gaps ◽  
Potential Formation ◽  
Lewis Adduct ◽  
Homo Lumo

This research targeted the synthesis of group 13 neutral heteroles via transmetallation of the tin atom in stannole moieties. The synthesis of Heteroles of 15a (1-chloro-2,3,4,5-tetraphenylborole), 15b (1-chloro-2,3,4,5-tetraphenylaluminole) and 15c (1-chloro-2,3,4,5-tetraphenylgallole) were attempted. The potential formation of Lewis base adducts were explored through the addition of a coordinating solvent of THF, Et3N, and Et2O and characterized with NMR (1H, 13C and 11B where applicable). It was attempted to synthesize Polymer 17a from the di-brominated borole monomer 16a via a Pd-catalyzed polycondensation reaction. THF was subsequently added to the polymer in an attempt to produce the polymer adduct 17a·THF. This was performed to produce a stable enough material for GPC analysis. The polymer was also characterized with NMR. Theoretical calculations were undertaken at the B3LYP/6-31G* level of DFT to help identify the effect of HOMO-LUMO energy gap of the above heteroles and their adducts. DFT calculations reveal that monomers and oligomer energy gaps can be tuned by substituents attached to the heterole, the type of Lewis adduct formed and the degree of catenation. These monomers and oligomers could potentially be novel building blocks for the synthesis of small energy gap π-conjugated systems.

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