ChemInform Abstract: Recent Applications of Aryltriazenes in Organic Synthesis via C-N/N-N Bond Cleavage

ChemInform ◽  
2015 ◽  
Vol 46 (31) ◽  
pp. no-no
Author(s):  
Yonghong Zhang ◽  
Dawei Cao ◽  
Wenbo Liu ◽  
Haiyan Hu ◽  
Xiaomei Zhang ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Bond Cleavage

Ultrasonically dispersed potassium in organic synthesis. Water-acceleration in reductive CS bond cleavage reactions

1991 ◽  
Vol 32 (29) ◽  
pp. 3551-3554 ◽  
Author(s):  
Ta-shue Chou ◽  
Shao-Hwa Hung ◽  
Man-Li Peng ◽  
Shwu-Jiaun Lee
Keyword(s):  
Organic Synthesis ◽  
Bond Cleavage ◽  
Cleavage Reactions

Activation of C–F, Si–F, and S–F Bonds by N-Heterocyclic Carbenes and Their Isoelectronic Analogues

Synlett ◽  
2020 ◽  
Vol 31 (14) ◽  
pp. 1349-1360 ◽  
Author(s):  
Eunsung Lee ◽  
Ewa Pietrasiak
Keyword(s):  
Nucleophilic Substitution ◽  
Organic Synthesis ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Main Group ◽  
Heterocyclic Carbenes ◽  
Full Potential ◽  
Short Summary ◽  
Special Case

Reactions involving C–F, Si–F, and S–F bond cleavage with N-heterocyclic carbenes and isoelectronic species are reviewed. Most examples involve activation of aromatic C–F bond via an SNAr pathway and nucleophilic substitution of fluorine in electron-deficient olefins. The mechanism of the C–F bond activation depends on the reaction partners and the reaction can proceed via addition–elimination, oxidative addition (concerted or stepwise) or metathesis. The adducts formed upon substitution find applications in organic synthesis, as ligands and as stable radical precursors, but in most cases, their full potential remains unexplored.1 Introduction1.1 The C–F Bond1.2 C–F Bond Activation: A Short Summary1.3 C–F Bond Activation: A Special Case of SNAr1.4 N-Heterocyclic Carbenes (NHCs)1.5 The Purpose of this Article2 C–F bond Activation in Acyl Fluorides3 Activation of Vinylic C–F Bonds4 Activation of Aromatic C–F Bonds5 X–F Bond Activation (X = S or Si)6 C–F Bond Activation by Main Group Compounds Isoelectronic with NHCs7 Conclusions and Outlook

Acyl iodides in organic synthesis: XI. Unusual N-C bond cleavage in tertiary amines

2008 ◽  
Vol 44 (4) ◽  
pp. 481-484 ◽  
Author(s):  
M. G. Voronkov ◽  
I. P. Tsyrendorzhieva ◽  
V. I. Rakhlin
Keyword(s):  
Organic Synthesis ◽  
Bond Cleavage ◽  
Tertiary Amines

Advances in Silylation and Borylation of Fluoroarenes and gem-Difluoroalkenes via C-F bond Cleavage

2021 ◽  
Author(s):  
Zhang Feng ◽  
Shasha Geng ◽  
Juan Zhang
Keyword(s):  
Organic Synthesis ◽  
Bond Cleavage ◽  
Bond Functionalization

Organoboron and organosilane compounds are widely used in organic synthesis and pharmaceuticals. In addition, the C-F bond functionalization is a useful tool for the construction of carbon-carbon and carbon-heteroatom bonds....

scholarly journals Electrochemical C-C Bond Cleavage of Cyclopropanes towards the Synthesis of 1,3-Difunctionalized Molecules

2020 ◽  
Author(s):  
Pan Peng ◽  
Xingxiu Yan ◽  
Ke Zhang ◽  
Zhao Liu ◽  
Li Zeng ◽  
...  
Keyword(s):  
Functional Groups ◽  
Organic Synthesis ◽  
Radical Cation ◽  
Redox Reactions ◽  
Bond Cleavage ◽  
Strategic Choice ◽  
Mechanistic Studies ◽  
Catalyst Free ◽  
Electrochemical Condition ◽  
Anode Oxidation

Abstract Electrochemistry had a lot of inherent advantages in organic synthesis and many redox reactions have been achieved under electrochemical condition. However, the electrochemical C-C bond cleavage and functionalization reactions are less studied. Here we developed electrochemical C-C bond cleavage and 1,3-difuntionalization of arylcyclopropanes under catalyst-free and external-oxidant-free conditions. 1,3-difluorination, 1,3-oxyfluorination and 1,3-dioxygenation of arylcyclopropanes were achieved with a highly chemo- and regioselectivity by the strategic choice of nucleophiles. This protocol has good functional groups tolerance and can be scaled up. Mechanistic studies demonstrate that arylcyclopropane radical cation yielded from the anode oxidation and the following generated benzyl carbonium are the key intermediates in this transformation. This development provides a new scenario for constructing 1,3-difunctionalized molecules.

scholarly journals σ-Bond Hydroboration of Cyclopropanes

2020 ◽  
Author(s):  
Hiroki Kondo ◽  
Shin Miyamura ◽  
Chisa Kobayashi ◽  
Arifin ◽  
Stephan Irle ◽  
...  
Keyword(s):  
Double Bond ◽  
Natural Product ◽  
Organic Synthesis ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
High Reactivity ◽  
Natural Product Synthesis ◽  
Theoretical Studies ◽  
Single Bond

Hydroboration of alkenes is a classical reaction in organic synthesis, in which alkenes react with boranes to give alkylboranes, with subsequent oxidation resulting in alcohols. The double bond (π-bond) of alkenes can be readily reacted with boranes owing to its high reactivity. However, the single bond (σ-bond) of alkanes has never been reacted. To pursue the development of σ-bond cleavage, we selected cyclopropanes as model substrates since they present a relatively weak σ-bond. Herein, we describe an iridium-catalyzed hydroboration of cyclopropanes, resulting in β-methyl alkylboronates. These unusually branched boronates can be derivatized by oxidation or cross-coupling chemistry, accessing “designer” products that are desired by practitioners of natural product synthesis and medicinal chemistry. Furthermore, mechanistic investigations and theoretical studies revealed the enabling role of the catalyst.

Alkyne-Forming Furan Fragmentation: A General Method to Convert Furans into Alkynoic Acids

Synlett ◽  
2019 ◽  
Vol 30 (06) ◽  
pp. 642-646
Author(s):  
Jinghan Gui ◽  
Jiachen Deng
Keyword(s):  
Reaction Mechanism ◽  
Double Bond ◽  
Singlet Oxygen ◽  
Natural Product ◽  
Organic Synthesis ◽  
Bond Cleavage ◽  
Historical Context ◽  
Natural Product Synthesis ◽  
Fragmentation Reaction ◽  
General Method

Furans are readily available and highly reactive heterocycles that serve as versatile four-carbon synthons in organic synthesis. Recently, we discovered that furans, upon oxidation with singlet oxygen, can be transformed into alkynes via dual C–C double-bond cleavage. This Synpacts article presents an overview of the historical context and the development of this furan fragmentation reaction. We also discuss its application in natural product synthesis and a plausible reaction mechanism.1 Introduction2 Background of Alkyne-Forming Furan Fragmentation3 Reaction Development4 Conclusion

Thioesterification and Selenoesterification of Amides via Selective N–C Cleavage at Room Temperature: N–C(O) to S/Se–C(O) Interconversion

Synthesis ◽  
2020 ◽  
Vol 52 (07) ◽  
pp. 1060-1066 ◽  
Author(s):  
Md. Mahbubur Rahman ◽  
Guangchen Li ◽  
Michal Szostak
Keyword(s):  
Transition Metals ◽  
Organic Synthesis ◽  
Ground State ◽  
Nucleophilic Addition ◽  
Room Temperature ◽  
Bond Cleavage ◽  
Tetrahedral Intermediate

The direct nucleophilic addition to amides represents an attractive methodology in organic synthesis that tackles amidic resonance by ground-state destabilization. This approach has been recently accomplished with carbon, nitrogen and oxygen nucleophiles. Herein, we report an exceedingly mild method for the direct thioesterification and selenoesterification of amides by selective N–C(O) bond cleavage in the absence of transition metals. Acyclic amides undergo N–C(O) to S/Se–C(O) interconversion to give the corresponding thioesters and selenoesters in excellent yields at room temperature via a tetrahedral intermediate pathway (cf. an acyl metal).

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