Iridium-catalyzed regio- and enantioselective allylic esterification of secondary allylic alcohols with carboxylic acids

2021 ◽  
Author(s):  
Shengbiao Tang ◽  
Peng Zhang ◽  
Changkai Wang ◽  
Ying Shao ◽  
Jiangtao Sun
Keyword(s):  
Carboxylic Acids ◽  
Functional Group ◽  
Allylic Alcohols ◽  
Mild Conditions

We report herein an iridium-catalyzed asymmetric allylic esterification of racemic secondary allylic alcohols with carboxylic acids under mild conditions with broad functional group tolerance, exhibiting excellent regio- (b/l > 19 : 1) and enantioselectivity (up to >99% ee).

Synthesis of O-Aroyl-N,N-dimethylhydroxylamines through Hypervalent Iodine-Mediated Amination of Carboxylic Acids with N,N-Dimethylformamide

Synthesis ◽  
2017 ◽  
Vol 49 (18) ◽  
pp. 4303-4308 ◽  
Author(s):  
Dong Li ◽  
Chuancheng Zhang ◽  
Qiang Yue ◽  
Zhen Xiao ◽  
Xianglan Wang ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Room Temperature ◽  
Functional Group ◽  
Hypervalent Iodine ◽  
Electrophilic Amination ◽  
Mild Conditions

An efficient protocol for the synthesis of O-aroyl-N,N-dimethylhydroxylamines, which are important electrophilic amination reagents, is described. The reaction between carboxylic acids and N,N-dimethylformamide is mediated by hypervalent iodine and occurs under mild conditions at room temperature to give the desired products in good yields. The process shows good functional group compatibility and air and moisture tolerance.

Construction of Esters through Sulfuryl Fluoride (SO2F2) Mediated Dehydrative Coupling of Carboxylic Acids with Alcohols at Room Temperature

Synthesis ◽  
2019 ◽  
Vol 51 (20) ◽  
pp. 3901-3907 ◽  
Author(s):  
Shi-Meng Wang ◽  
Njud S. Alharbi ◽  
Hua-Li Qin
Keyword(s):  
Carboxylic Acids ◽  
Room Temperature ◽  
Functional Group ◽  
High Efficiency ◽  
Sulfuryl Fluoride ◽  
Mild Conditions ◽  
High Yields

A facile method for the construction of esters through dehydrative coupling of carboxylic acids with alcohols is developed. The reactions are mediated by sulfuryl fluoride (SO2F2) at room temperature and proceed with high efficiency. The method has several advantages including broad substrate scope, mild conditions, excellent functional group compatibility and affords high yields, even on gram scale.

Nickel-catalyzed carboxylation of aryl iodides with lithium formate through catalytic CO recycling

2020 ◽  
Vol 56 (29) ◽  
pp. 4067-4069 ◽  
Author(s):  
Ya-Nan Wu ◽  
Ming-Chen Fu ◽  
Rui Shang ◽  
Yao Fu
Keyword(s):  
Carboxylic Acids ◽  
Functional Group ◽  
Aromatic Carboxylic Acids ◽  
Mild Conditions ◽  
Aryl Iodides ◽  
Lithium Formate

A protocol for the Ni-catalyzed carboxylation of aryl iodides with formate has been developed with good functional group compatibility for the synthesis of a variety of aromatic carboxylic acids under mild conditions.

scholarly journals Dual-Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules

2018 ◽  
Author(s):  
Dawid Lichosyt ◽  
Yang Zhang ◽  
Karolina Hurej ◽  
Pawel Dydio
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Functional Group ◽  
Aliphatic Alcohols ◽  
Catalytic Reactions ◽  
Allylic Alcohols ◽  
Catalytic Systems ◽  
Mild Conditions ◽  
Broad Scope ◽  
Activation Cycle

<b>Catalytic reactions occur readily at sites of starting materials that are both innately reactive and sterically accessible or that are predisposed by a functional group amenable to direct a catalyst. However, selective reactions at unbiased sites of substrates remain challenging and typically require additional pre-activation steps or the use of highly reactive reagents. Herein, we report dual-catalytic transition metal systems that merge a reversible activation cycle with a functionalization cycle, together enabling functionalization of substrates at their inherently unreactive sites. By engaging the Ru- or Fe-catalyzed equilibrium between an alcohol and an aldehyde, Pd-catalyzed <i>b</i>-arylation of aliphatic alcohols and Rh-catalyzed <i>g</i>-hydroarylation of allylic alcohols were developed. The mild conditions, functional group tolerance and broad scope of the methodologies (81 examples) demonstrate the synthetic applicability of the dual-catalytic systems. In a broader context, this work highlights the potential of the multi-catalytic approach to address challenging transformations to circumvent the multi-step procedures and the use of highly reactive reagents in organic synthesis.</b>

scholarly journals Dual-Catalytic Transition Metal Systems for Functionalization of Unreactive Sites of Molecules

2018 ◽  
Author(s):  
Dawid Lichosyt ◽  
Yang Zhang ◽  
Karolina Hurej ◽  
Pawel Dydio
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Functional Group ◽  
Aliphatic Alcohols ◽  
Catalytic Reactions ◽  
Allylic Alcohols ◽  
Catalytic Systems ◽  
Mild Conditions ◽  
Broad Scope ◽  
Activation Cycle

<b>Catalytic reactions occur readily at sites of starting materials that are both innately reactive and sterically accessible or that are predisposed by a functional group amenable to direct a catalyst. However, selective reactions at unbiased sites of substrates remain challenging and typically require additional pre-activation steps or the use of highly reactive reagents. Herein, we report dual-catalytic transition metal systems that merge a reversible activation cycle with a functionalization cycle, together enabling functionalization of substrates at their inherently unreactive sites. By engaging the Ru- or Fe-catalyzed equilibrium between an alcohol and an aldehyde, Pd-catalyzed <i>b</i>-arylation of aliphatic alcohols and Rh-catalyzed <i>g</i>-hydroarylation of allylic alcohols were developed. The mild conditions, functional group tolerance and broad scope of the methodologies (81 examples) demonstrate the synthetic applicability of the dual-catalytic systems. In a broader context, this work highlights the potential of the multi-catalytic approach to address challenging transformations to circumvent the multi-step procedures and the use of highly reactive reagents in organic synthesis.</b>

Practical allylation with unactivated allylic alcohols under mild conditions

2021 ◽  
Author(s):  
Shuangshuang Li ◽  
Ju Qiu ◽  
Bowen Li ◽  
Zuolian Sun ◽  
Peizhong Xie ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Catalytic System ◽  
Allylic Alcohols ◽  
Mild Conditions ◽  
Accelerate Proton

A practical palladium/calcium catalytic system was developed for dehydrative allylation concerning unactivated allylic alcohols. EtOH solvent with H2O additive was identified as powerful media to accelerate proton transfer. That catalytic...

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Synlett ◽  
2021 ◽  
Author(s):  
Xianqing Wu ◽  
Mohini Shrestha ◽  
Yifeng Chen
Keyword(s):  
Functional Group ◽  
Enantioselective Synthesis ◽  
Chiral Auxiliary ◽  
Alkyl Iodide ◽  
General Strategy ◽  
Chemical Bonds ◽  
Mild Conditions ◽  
Chiral Carbon ◽  
Enantioselective Reaction ◽  
Metal Catalyzed

AbstractChiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

Rh (III)-catalyzed C(sp2)-H functionalization/cyclization cascade of N-carboxamide indole and iodonium reagent for access to indoloquinazolinone derivatives

2021 ◽  
Author(s):  
Zhi-Peng Han ◽  
Mengmeng Xu ◽  
Rui-Ying Zhang ◽  
Xiao-Ping Xu ◽  
Shun-Jun Ji
Keyword(s):  
Functional Group ◽  
Mild Conditions

Rhodium-catalyzed synthesis of indoloquinazoline from readily available hypervalent iodonium reagent and N-carboxamide indole was developed. The protocol features broad functional group tolerance, mild conditions, excellent yields and simple workup. Notably,...

scholarly journals Mechanically induced solvent-free esterification method at room temperature

RSC Advances ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 5080-5085
Author(s):  
Lei Zheng ◽  
Chen Sun ◽  
Wenhao Xu ◽  
Alexandr V. Dushkin ◽  
Nikolay Polyakov ◽  
...  
Keyword(s):  
Natural Products ◽  
Carboxylic Acids ◽  
Late Stage ◽  
Reaction Mechanisms ◽  
Room Temperature ◽  
Solvent Free ◽  
Mild Conditions

We have developed I2/KH2PO2 and KI/P(OEt)3 strategy syntheses of esters from carboxylic acids and alcohols through different reaction mechanisms. The advantages of present protocol: mild conditions and late-stage diversification of natural products.

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