An efficient way for the N-formylation of amines by inorganic-ligand supported iron catalysis

organic chemistry, SYNTHESIS Comments Off

Jan 162020

Graphical abstract: An efficient way for the N-formylation of amines by inorganic-ligand supported iron catalysis

An efficient way for the N-formylation of amines by inorganic-ligand supported iron catalysis

Green Chem., 2020, Advance Article

DOI: 10.1039/C9GC03564H, Paper

Zhikang Wu, Yongyan Zhai, Wenshu Zhao, Zheyu Wei, Han Yu, Sheng Han, Yongge Wei
A green and highly efficient N-formylation of amines using formic acid as the acylating agent by iron catalysis with excellent selectivity and yields.
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An efficient way for the N-formylation of amines by inorganic-ligand supported iron catalysis

Zhikang Wu,‡^a Yongyan Zhai,‡^a Wenshu Zhao,‡^b Zheyu Wei,^a Han Yu,*^ac Sheng Han

*^a and Yongge Wei

*^cd

Author affiliations

*Corresponding authors

^aSchool of Chemical and Environmental Engineering Shanghai Institute of Technology, No. 100 Haiquan Road, Shanghai 201418, P.R. China
E-mail: hanyu0220@tsinghua.edu.cn, hansheng654321@sina.com

^bLonghua Hospital Shanghai University of Traditional Chinese Medicine, China

^cKey Lab of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, P.R. China
E-mail: yonggewei@tsinghua.edu.cn

^dState Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing 100191, P.R. China
E-mail: ygwei@pku.edu.cn

Abstract

The first example of an inorganic-ligand supported iron(III) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH₄)₃[FeMo₆O₁₈(OH)₆] (1), which consists of a central Fe^III single-atomic core supported within a cycle-shaped inorganic ligand consisting of six Mo^VIO₆ octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.

Image result for Zhikang Wu School of Chemical and Environmental Engineering Shanghai Institute of Technology, No. 100 Haiquan Road, Shanghai 201418, P.R. China

////////////https://pubs.rsc.org/en/Content/ArticleLanding/2020/GC/C9GC03564H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

http://www.rsc.org/suppdata/c9/gc/c9gc03564h/c9gc03564h1.pdf

Catalyst- and Additive-Free Baeyer−Villiger-type Oxidation of α-Iodocyclopentenones to α-Pyrones: Using Air as the Oxidant

ANTHONY CRASTO, organic chemistry, spectroscopy, SYNTHESIS Comments Off

Sep 112019

Catalyst- and Additive-Free Baeyer−Villiger-type Oxidation of α-Iodocyclopentenones to α-Pyrones: Using Air as the Oxidant

Yuanyuan Zhou, Xianxiao Chen, Xiangxiang Ling and Weidong Rao

Abstract

An efficient synthetic approach for the synthesis of α-pyrones via Baeyer−Villiger-type oxidation of α-iodocyclopentenones through a catalyst- and additive-free system using air as an environmentally benign oxidant is described. The reaction exhibits excellent functional group compatibility and provides a simple and efficient protocol for the construction of highly functionalized α-pyrones under mild reaction conditions.

Ethyl 4-(4-cyclopropyl-2-oxo-2H-pyran-6-yl)butanoate (2aa) Product 2aa was obtained as yellow oil in 50% yield (38 mg) following the general procedure; 1H NMR (600 MHz, CDCl3) δ 5.84 (s, 1H), 5.61 (s, 1H), 4.13-4.09 (m, 2H), 2.48 (t, J = 7.3 Hz, 2H), 2.33 (td, J = 7.3, 2.3 Hz, 2H), 1.97-1.94 (m, 2H), 1.66-1.63 (m, 1H), 1.26-1.22 (m, 3H), 1.07-1.05 (m, 2H), 0.80-0.79 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 172.8, 163.9, 163.0, 162.8, 106.7, 102.1, 60.5, 33.2, 33.0, 22.1, 15.4, 14.2, 10.0; HRMS (ESI) calcd. for C14H18O4Na [M+Na]+ : 273.1097, found: 273.1101

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https://pubs.rsc.org/en/Content/ArticleLanding/2019/GC/C9GC02725D?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

http://www.rsc.org/suppdata/c9/gc/c9gc02725d/c9gc02725d1.pdf

Triple copper catalysis for the synthesis of vinyl triazoles

green chemistry, organic chemistry Comments Off

Jul 012019

Triple copper catalysis for the synthesis of vinyl triazoles

Green Chem., 2019, Advance Article
DOI: 10.1039/C9GC01066A, Communication

Lucas L. Baldassari, Eduardo A. Cechinatto, Angélica V. Moro
Herein, we report our studies on the synthesis of vinyl 1,2,3-triazoles through a one-pot sequence, enabled by the same copper catalyst, of three different reactions: hydroboration involving an alkyne, azidation for a vinyl boronate and azide–alkyne cycloaddition.
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Triple copper catalysis for the synthesis of vinyl triazoles

Lucas L. Baldassari,^a Eduardo A. Cechinatto^a and Angélica V. Moro*^a

Author affiliations

*Corresponding authors

^aInstitute of Chemistry, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, Porto Alegre, Brazil
E-mail:angelica.venturini@ufrgs.br
Fax: +5551 3308 6259
Tel: +55 51 3308 9637

Abstract

Herein, we report our studies on the synthesis of vinyl 1,2,3-triazoles through a one-pot sequence, enabled by the same copper catalyst, of three different reactions: hydroboration involving an alkyne, azidation for a vinyl boronate and azide–alkyne cycloaddition.

https://pubs.rsc.org/en/Content/ArticleLanding/2019/GC/C9GC01066A?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

///////copper catalysis, vinyl triazoles

Basic Anion-Exchange Resin-Catalyzed Aldol Condensation of Aromatic Ketones with Aldehydes in Continuous Flow

organic chemistry, PROCESS Comments Off

Apr 262019

A general method for the aldol condensation of aromatic ketones with aldehydes was developed under continuous-flow conditions using a commercially available, strongly basic anion-exchange resin (A26) as catalyst. This procedure, in addition to exhibiting a wide substrate scope, promoted carbon–carbon bond formation under mild conditions using a quasi-stoichiometric ratio of starting reagents with good to excellent yields, thereby forming a limited amount of waste and allowing the process to be applied to sequential-flow systems. A proof of concept was developed in the first fully heterogeneously catalyzed two-step flow synthesis of donepezil, which is a blockbuster commercial anti-Alzheimer’s drug.

Basic Anion-Exchange Resin-Catalyzed Aldol Condensation of Aromatic Ketones with Aldehydes in Continuous Flow

Benjamin Laroche^†, Yuki Saito^†, Haruro Ishitani^‡, and Shu̅ Kobayashi*^†^‡

^†Department of Chemistry, School of Science, and ^‡Green & Sustainable Chemistry Social Cooperation Laboratory, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.9b00048

*E-mail: shu_kobayashi@chem.s.u-tokyo.ac.jp.

https://pubs.acs.org/doi/10.1021/acs.oprd.9b00048

////////donepezil

Structural evolution of carbon in an Fe@C catalyst during the Fischer–Tropsch synthesis reaction

ANTHONY CRASTO, organic chemistry, SYNTHESIS Comments Off

Feb 012019

Structural evolution of carbon in an Fe@C catalyst during the Fischer–Tropsch synthesis reaction

Shuai Lyu,^a^b Chengchao Liu,^b Guanghui Wang,*^a Yuhua Zhang,^b Jinlin Li^b and Li Wang*^b

Author affiliations

*Corresponding authors

^aHubei Key Laboratory of Coal Conversion and New Carbon Material, School of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, China
E-mail: wghwang@263.net

^bKey Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, South-Central University for Nationalities, Wuhan 430074, China
E-mail: li.wang@mail.scuec.edu.cn

Abstract

A pseudo-in situ research method was applied to provide insight into the structural evolution of carbon in an Fe@C catalyst at different stages of the Fischer–Tropsch reaction. Five typical stages of the catalyst were selected for in-depth structural investigation; these were: the fresh catalyst, reduced catalyst, and catalyst in the stable conversion period, in an increased-conversion period and at the inactivation stage. The results indicated that the integral structure of Fe@C constantly changed in the Fischer–Tropsch reaction. Iron carbide transformed from the Fe phase that was easily oxidized under high temperature Fischer–Tropsch conditions, and the carbon framework was completely destroyed in the reaction process, leading to a drastic decrease in the specific surface area of the material. This destruction could have two opposing effects: on the one hand, the loss of carbon could re-expose the active sites that have been covered by carbon at a reaction temperature of 320 °C and favor the reaction; on the other hand, the deposition of carbon could block the active sites and lead to inactivation when the reaction temperature is over 340 °C.

https://pubs.rsc.org/en/Content/ArticleLanding/2019/CY/C8CY02420K?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2Fcy+%28RSC+-+Catalysis+Science+%26+Technology+latest+articles%29#!divAbstract

////////Fischer–Tropsch

Photo-organocatalytic synthesis of acetals from aldehydes

organic chemistry, spectroscopy, SYNTHESIS Comments Off

Jan 292019

Graphical abstract: Photo-organocatalytic synthesis of acetals from aldehydes

Abstract

A mild and green photo-organocatalytic protocol for the highly efficient acetalization of aldehydes has been developed. Utilizing thioxanthenone as the photocatalyst and inexpensive household lamps as the light source, a variety of aromatic and aliphatic aldehydes have been converted into acyclic and cyclic acetals in high yields. The reaction mechanism was extensively studied

Photo-organocatalytic synthesis of acetals from aldehydes

Nikolaos F. Nikitas,^a Ierasia Triandafillidi^a and Christoforos G. Kokotos*^a

Author affiliations

*Corresponding authors

^aLaboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, Athens 15771, Greece
E-mail:ckokotos@chem.uoa.gr

https://pubs.rsc.org/en/Content/ArticleLanding/2019/GC/C8GC03605E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

(3,3-Dimethoxypropyl)benzene (2a)6

Colorless oil; 95% yield; 1H NMR (200 MHz, CDCl3) δ: 7.33-7.18 (5H, m, ArH), 4.37 (1H, t, J = 5.8 Hz, OCH), 3.33 (6H, s, 2 x OCH3), 2.68 (2H, t, J = 7.6 Hz, CH2), 1.98- 1.87 (2H, m, CH2); 13C NMR (50 MHz, CDCl3) δ: 141.8, 128.4, 125.9, 103.7, 52.8, 34.0, 30.8; MS (ESI) m/z 181 [M+H]+ .

6. Q. Zhou, T. Jia. X.-X. Li, L. Zhou, C.-J. Li, Y. S. Feng, Synth. Commun., 2018, 48, 1068.

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Development of an SNAr Reaction: A Practical and Scalable Strategy To Sequester and Remove HF

organic chemistry, SYNTHESIS Comments Off

Sep 142018

Abstract Image

A simple and operationally practical method to sequester and remove fluoride generated through the S_NAr reaction between amines and aryl fluorides is reported. Calcium propionate acts as an inexpensive and environmentally benign in situ scrubber of the hydrofluoric acid byproduct, which is simply precipitated and filtered from the reaction mixture during standard aqueous workup. The method has been tested from 10 to 100 g scale of operation, showing >99.5% decrease in fluoride content in each case. Full mass recovery of calcium fluoride is demonstrated at both scales, proving this to be a general, efficient, and robust method of fluoride abstraction to help prevent corrosion of glass-lined reactors.

Development of an S_NAr Reaction: A Practical and Scalable Strategy To Sequester and Remove HF

A. John Blacker*^†

, Gabriel Moran-Malagon^†, Lyn Powell^‡, William Reynolds^†, Rebecca Stones^†, and Michael R. Chapman^†

^† Institute of Process Research and Development, School of Chemistry and School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, United Kingdom

^‡ Chemical Development, AstraZeneca, Macclesfield SK10 2NA, United Kingdom

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.8b00090

*E-mail: j.blacker@leeds.ac.uk.

///////////////aryl amines, calcium fluoride, fluoride sequestration, scale-up, S_NAr reaction,

“ALL FOR DRUGS” CATERS TO EDUCATION GLOBALLY, No commercial exploits are done or advertisements added by me. This is a compilation for educational purposes only. P.S. : The views expressed are my personal and in no-way suggest the views of the professional body or the company that I represent

Process Development of Febuxostat Using Palladium- and Copper-Catalyzed C–H Arylation

MANUFACTURING, organic chemistry, spectroscopy, SYNTHESIS Comments Off

Sep 112018

There is significant interest in the development of process routes for active pharmaceutical ingredients using C–H arylation methodology. An efficient and practical synthetic route for febuxostat (1), which is the first non-purine-type xanthine oxidase inhibitor, was established via palladium- and copper-catalyzed C–H arylation of thiazole with aryl bromide. The catalyst loading was reduced to 0.1 mol % for the intermolecular C–H arylation, and a three-step synthesis produced febuxostat in 89% overall yield with excellent selectivity

Process Development of Febuxostat Using Palladium- and Copper-Catalyzed C–H Arylation

Masato Komiyama*

, Hideyoshi Tsuchiya, Mitsuru Teramoto, Naoki Yajima, Masayuki Kurokawa, Kunio Minamizono, Naoki Tsuchiya, Yoshiaki Kato, Yoshinori Sato, and Masahiko Dohi

Active Pharmaceutical Ingredient Technology Section, Pharmaceutical Preparation Department, Teijin Pharma Limited, 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi 740-8511, Japan

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.8b00164

*E-mail: m.komiyama@teijin.co.jp.

https://pubs.acs.org/doi/10.1021/acs.oprd.8b00164

1 (22.5 g, 98%) as a whitish solid. ¹H NMR (400 MHz, CDCl₃): δ 8.20 (d, J = 2.4 Hz, 1H), 8.11 (dd, J = 9.0 Hz, 2.4 Hz, 1H), 7.03 (d, J = 9.0 Hz, 1H), 3.91 (d, J = 6.6 Hz, 2H), 2.80 (s, 3H), 2.23–2.20 (m, 1H), 1.20 (d, J = 6.8 Hz, 6H).

//////FEBUXOSTAT

Ethyl 4, 6-dichloro-1H-indole-2-carboxylate

organic chemistry, spectroscopy, SYNTHESIS Comments Off

Aug 282018

Ethyl 4, 6-dichloro-1H-indole-2-carboxylate

ethyl 4,6-dichloro-1H-indole-2-carboxylate (1a) (2.70 kg, 99.5%).

Mp 187–188 °C; HRMS (ESI) m/z [M – H]⁻ calcd for C₁₁H₈NO₂Cl₂ 255.9927, found 255.9930;

¹H NMR (400 MHz, DMSO-d₆) δ 12.41 (s, 1H), 7.44 (s, 1H), 7.27 (s, 1H), 7.10 (s, 1H), 4.43–4.30 (q, 2H), 1.34 (d, 3H);

¹³C NMR (151 MHz, CDCl₃) δ 161.69, 137.08, 131.00, 128.45, 128.37, 125.31, 121.26, 110.52, 107.07, 61.56, 14.32;

IR (cm^–1) 3314.3, 2987.6, 1700.2, 1615.8, 1566.2, 1523.7, 1487.2, 1323.3, 1247.2, 1072.4, 840.1, 770.2.

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.8b00144

https://pubs.acs.org/doi/10.1021/acs.oprd.8b00144

https://pubs.acs.org/doi/suppl/10.1021/acs.oprd.8b00144/suppl_file/op8b00144_si_001.pdf

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A versatile biosynthetic approach to amide bond formation

organic chemistry, SYNTHESIS Comments Off

Aug 022018

Graphical abstract: A versatile biosynthetic approach to amide bond formation

A versatile biosynthetic approach to amide bond formation

Helena K. Philpott,^a Pamela J. Thomas,^b David Tew,^a Doug E. Fuerst^c and Sarah L. Lovelock*^a

Author affiliations

*Corresponding authors

^aAdvanced Manufacturing Technologies, GlaxoSmithKline, Medicines Research Centre, Gunnels Wood Road, Stevenage, UK
E-mail: sarah.lovelock@manchester.ac.uk

^bMolecular Design, Computational and Modelling Sciences, GlaxoSmithKline, Medicines Research Centre, Gunnels Wood Road, Stevenage, UK

^cAdvanced Manufacturing Technologies, GlaxoSmithKline, 709 Swedeland Road, King of Prussia, USA

Abstract

The development of versatile and sustainable catalytic strategies for amide bond formation is a major objective for the pharmaceutical sector and the wider chemical industry. Herein, we report a biocatalytic approach to amide synthesis which exploits the diversity of Nature’s amide bond forming enzymes, N-acyltransferases (NATs) and CoA ligases (CLs). By selecting combinations of NATs and CLs with desired substrate profiles, non-natural biocatalytic pathways can be built in a predictable fashion to allow access to structurally diverse secondary and tertiary amides in high yield using stoichiometric ratios of carboxylic acid and amine coupling partners. Transformations can be performed in vitro using isolated enzymes, or in vivo where reactions rely solely on cofactors generated by the cell. The utility of these whole cell systems is showcased through the preparative scale synthesis of a key intermediate of Losmapimod (GW856553X), a selective p38-mitogen activated protein kinase inhibitor.

http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C8GC01697F?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

////////////biosynthetic, amide bond