1,1'-(4'-(tert-butoxy)-4-(dimethylamino)-[1,1'-biphenyl]-2,6-diyl)diethanone

1,1'-(4'-(tert-butoxy)-4-(dimethylamino)-[1,1'-biphenyl]-2,6-diyl)diethanone

NMR IS EASY

MOM CAN TEACH

13C NMR PREDICT

CC(C)(C)Oc1ccc(cc1)c2c(cc(cc2C(C)=O)N(C)C)C(C)=O

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“ORG SPECT INT” 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

Gram-Scale Synthesis of Amines Bearing a gem-Difluorocyclopropane Moiety

Ukraine

Abstract

The synthesis of monocyclic, spirocyclic and fused bicyclic secondary amines bearing a gem-difluorocyclopropane moiety via difluorocyclopropanation of unsaturated N-Boc derivatives using the trifluoromethyl(trimethyl)silane/sodium iodide [CF₃SiMe₃-NaI] system is described. The relative order of the substrate reactivity is established. It is shown that for the reactive alkenes the standard reaction conditions can be used, whereas for the substrates with low reactivity, slow addition of the Ruppert–Prakash reagent is necessary.

Gram-Scale Synthesis of Amines Bearing a gem-Difluorocyclopropane Moiety

Authors., Pavel S. Nosik,

DOI: 10.1002/adsc.201700857

Pavel S. Nosik,a.b Andrii O. Gerasov,a Rodion O. Boiko,a Eduard Rusanov,b Sergey V. Ryabukhin,c Oleksandr O. Grygorenko,c * Dmitriy M. Volochnyukb
a Spectrum Info Ltd., Life Chemicals Inc., Murmanska Street 5, Kyiv 02094, Ukraine

b Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, Ukraine

c National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

* Corresponding author. E-mail: gregor@univ.kiev.ua.

Oleksandr Grygorenko

Ph D

Professor (Associate)

National Taras Shevchenko Univ... , Kiev · Faculty of Chemistry

National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, Kyiv 01601, Ukraine

National Taras Shevchenko University of Kyiv

Department

• Faculty of Chemistry

Dmitriy M. Volochnyuk

Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, Ukraine
Dmitriy M. Volochnyuk was born in 1980 in Irpen, Kyiv region, Ukraine. He graduated from Kyiv State Taras Shevchenko University in 2002 and was awarded his M.S. degree in chemistry. He received his Ph.D. in organic chemistry in 2005 from the Institute of Organic Chemistry, National Academy of Sciences of Ukraine under the supervision of Dr. A. Kostyuk for research on the chemistry of enamines. At present, he divides his time between the Institute of Organic Chemisty, as Deputy Head of Organophosphorus Department and Senior Researcher, and Enamine Ltd (Kyiv, Ukraine), as Director of Chemistry. His main scientific interests are related to fluoroorganic, organophosphorus, heterocyclic and combinatorial chemistry, and multistep organic synthesis. He is a coauthor of more than 80 papers

• Given that the incorporation of small fluorinated fragments in drug-like molecules continues to rise, this has created an onus on the synthetic community to provide robust, scalable routes to these molecules of interest. Grygorenko and co-workers have reported on a synthesis of amines featuring a gem-difluorocyclopropane moiety using the readily available Ruppert–Prakash reagent ( Adv. Synth. Catal. 2017, 10.1002/adsc.201700857).
• Evaluating a series of olefins under the standard reaction conditions in refluxing THF indicated that only the most reactive olefins (gem-disubstituted) provided good yields of the desired cyclopropane, while other solvents proved to be ineffective. Conducting a control experiment omitting the substrate demonstrated that the key issue herein was competitive decomposition of the TMSCF₃ to a series of gaseous byproducts under the reaction conditions.
• Whereas continuous flow provides a potential to mitigate against this, the current report demonstrated that slow addition of the reagent to the reaction mixture also provided a practical solution to this problem.
• Employing this approach enabled not only excellent conversions and yields to be realized but also allowed reactivity trends to be identified. In general, gem-disubstituted are the most reactive with the trend correlating with steric hindrance.
• For other classes of olefins, electronics are the major factor with the ability of the substituents to stabilize a positive charge in the transition state consistent with a nonsynchronous formation of the two sigma bonds in the cycloaddition the key consideration. The removal of the Boc-protecting group under standard acidic conditions provided the amines as their hydrochloride salts.
• 

• Eduard Rusanov

  PhD

  Head of Crystallographic Lab./Director of the crystallographic facility Nat. Acad. of Sci. Ukraine 'Single Mjlecule Crystallography' at IOC

  Institute of Organic Chemistry... · DEPARTMENT OF PHYSICOCHEMICAL INVESTIGATIONS
   

tert-Butyl 1,1-difluoro-6-azaspiro[2.5]octane-6-carboxylate (10a):

Yield: 66.7 g (91%) (Method A); off-white crystalline powder: mp 46–48 8C;

1H NMR (CDCl3 , 400 MHz): d= 3.57–3.42 (m, 2H), 3.40–3.27 (m, 2H), 1.66–1.47 (m, 4H), 1.44 (s, J=2.3 Hz, 9H), 1.08 (t, J=8.3 Hz, 2H);

13C NMR (CDCl3, 101 MHz): d=154.2, 115.4 (t, J=288.1 Hz), 79.3, 42.8, 28.4, 28.1, 26.8 (t, J=10.0 Hz), 21.0 (t, J=10.1 Hz);

19F NMR (CDCl3 , 376 MHz): d=@140.6;

MS (EI): m/z= 247 (M+ ), 192 (M+@t-Bu), 174 (M+@t-BuO), 147 (M+@Boc), 127 (M+@Boc@HF);

Anal. calcd. for C12H19F2NO2 : C 58.29, H 7.74, N 5.66; found: C 58.49, H 8.02, N 5.30.

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Zhong-Xia WANG

N,N-dimethyl-4-biphenylamine

 

 

Molecular Formula, C₁₄H₁₅N

 

Molecular Weight, 197.28

 

CAS Number, 1137-79-7

(1) N,N-dimethyl-[1,1'-biphenyl]-4-amine (3a) 5,6

Elute: EtOAc/petroleum ether: 1/100 (v/v), white solid, yield 97.8 mg (99%).

1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 8.8 Hz, 2H), 7.40 (t, J = 7.7 Hz, 2H), 7.30–7.21 (m, 1H), 6.81 (d, J = 8.8 Hz, 2H), 3.00 (s, 6H).

13C NMR (101 MHz, CDCl3): δ 150.09, 141.34, 129.37, 128.78, 127.84, 126.43, 126.12, 112.90, 40.97.

5 Yang, X.; Wang, Z.-X. Organometallics 2014, 33, 5863.

(6) Stibingerova, I.; Voltrova, S.; Kocova, S.; Lindale, M.; Srogl, J. Org. Lett. 2016, 18, 312.

 

Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents

Bo Yang^† and Zhong-Xia Wang^*†‡ 

^† CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

^‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.7b03145

 

*E-mail: zxwang@ustc.edu.cn.

Abstract

Cross-coupling of (hetero)arylthiols with arylzinc reagents via C–S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg²⁺ and Li⁺ ions were demonstrated to facilitate the reaction.

In summary, we developed a transition-metal-free coupling reaction of (hetero)arylthiols with arylzinc reagents to form bi(hetero)aryls. The reaction exhibited wide substrate scope and good compatibility of functional groups. Electron-rich and -poor aryl or heteroaryl thiols can be converted. Various arylzinc reagents, including electron-rich and electron-poor reagents, can be employed as the coupling partners. Preliminary mechanistic studies suggest a nucleophilic aromatic substitution pathway, and Mg²⁺ and Li⁺ ions play important roles in the process of reaction. This study provides an example of S^2– as a leaving group in an aromatic system and an effective methodology for the synthesis of bi(hetero)aryls including pharmaceutical molecules without transition-metal impurities.

Zhong-Xia WANG       Department： Department of Chemistry Mailing Address： Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Rd, Hefei, Anhui, 230026, PR China Postal Code： 230026 Phone： +86-551-63603043 Fax：   Homepage： http://chem.ustc.edu.cn/szdw_16/bd/201210/t20121023_142877.html

Zhong-Xia Wang is a professor in the Department of Chemistry at the University of Science and Technology 
of China. He received his BS degree (1983) and MS degree (1986) from Nankai University, 
and PhD degree (1997) from the University of Sussex, UK. Since July 1986, Wang has been working 
at the University of Science and Technology of China (USTC) successively as Assistant, 
Lecturer, Associate Professor, and Professor. From Aug. 1993 to Oct. 1996, he pursued his doctoral 
studies at the University of Sussex, UK, and from Oct. 1999 to Oct. 2000, he was a Research Associate 
at the Chinese University of Hong Kong.

 学 系
Department of Chemistry

Predicts

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http://pubs.acs.org/doi/10.1021/acs.orglett.7b03145

“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

Zhong-Xia WANG

N,N-dimethyl-4-biphenylamine

 

 

Molecular Formula, C₁₄H₁₅N

 

Molecular Weight, 197.28

 

CAS Number, 1137-79-7

(1) N,N-dimethyl-[1,1'-biphenyl]-4-amine (3a) 5,6

Elute: EtOAc/petroleum ether: 1/100 (v/v), white solid, yield 97.8 mg (99%).

1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 8.8 Hz, 2H), 7.40 (t, J = 7.7 Hz, 2H), 7.30–7.21 (m, 1H), 6.81 (d, J = 8.8 Hz, 2H), 3.00 (s, 6H).

13C NMR (101 MHz, CDCl3): δ 150.09, 141.34, 129.37, 128.78, 127.84, 126.43, 126.12, 112.90, 40.97.

5 Yang, X.; Wang, Z.-X. Organometallics 2014, 33, 5863.

(6) Stibingerova, I.; Voltrova, S.; Kocova, S.; Lindale, M.; Srogl, J. Org. Lett. 2016, 18, 312.

 

Transition-Metal-Free Cross-Coupling of Aryl and Heteroaryl Thiols with Arylzinc Reagents

Bo Yang^† and Zhong-Xia Wang^*†‡ 

^† CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

^‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.7b03145

 

*E-mail: zxwang@ustc.edu.cn.

Abstract

Cross-coupling of (hetero)arylthiols with arylzinc reagents via C–S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg²⁺ and Li⁺ ions were demonstrated to facilitate the reaction.

In summary, we developed a transition-metal-free coupling reaction of (hetero)arylthiols with arylzinc reagents to form bi(hetero)aryls. The reaction exhibited wide substrate scope and good compatibility of functional groups. Electron-rich and -poor aryl or heteroaryl thiols can be converted. Various arylzinc reagents, including electron-rich and electron-poor reagents, can be employed as the coupling partners. Preliminary mechanistic studies suggest a nucleophilic aromatic substitution pathway, and Mg²⁺ and Li⁺ ions play important roles in the process of reaction. This study provides an example of S^2– as a leaving group in an aromatic system and an effective methodology for the synthesis of bi(hetero)aryls including pharmaceutical molecules without transition-metal impurities.

Zhong-Xia WANG       Department： Department of Chemistry Mailing Address： Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Rd, Hefei, Anhui, 230026, PR China Postal Code： 230026 Phone： +86-551-63603043 Fax：   Homepage： http://chem.ustc.edu.cn/szdw_16/bd/201210/t20121023_142877.html

Zhong-Xia Wang is a professor in the Department of Chemistry at the University of Science and Technology 
of China. He received his BS degree (1983) and MS degree (1986) from Nankai University, 
and PhD degree (1997) from the University of Sussex, UK. Since July 1986, Wang has been working 
at the University of Science and Technology of China (USTC) successively as Assistant, 
Lecturer, Associate Professor, and Professor. From Aug. 1993 to Oct. 1996, he pursued his doctoral 
studies at the University of Sussex, UK, and from Oct. 1999 to Oct. 2000, he was a Research Associate 
at the Chinese University of Hong Kong.

 学 系
Department of Chemistry

Predicts

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http://pubs.acs.org/doi/10.1021/acs.orglett.7b03145

“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

2-Phenylfuran

2-Phenylfuran

17113-33-6 cas

 

2-Phenylfuran (3v) [15]: According to the general procedure I and purification by column chromatography (100% PE) yielded 3v (35.9 mg, 50%) and the general procedure II yielded 3s (35.1 mg, 49%) as a white solid . 1 H NMR (400 MHz, CDCl3) δ 7.68-7.66 (m 2H), 7.46 (s, 1H), 7.40-7.35 (m, 2H), 7.26-7.23 (m, 1H), 6.645-6.639 (m, 1H), 6.461-6.457 (m, 1H). LRMS (ESI) calcd for [M+H]+ C10H9O 145.1, found 145.1.

15 Zhou, C.-Y.; Chan, P. W. H.; Che, C.-M. Org. Lett. 2006, 8, 325.

Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides

Yannan Cheng, Xiangyong Gu, and Pixu Li*

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering, and Materials Science, Soochow University, 199 RenAi Road, Suzhou, Jiangsu 215123, China

Org. Lett., 2013, 15 (11), pp 2664–2667

DOI: 10.1021/ol400946k

 

lipixu@suda.edu.cn

Abstract

Direct arylation of unactivated arenes or heteroarenes with aryl halides could be carried out in the presence of potassium tert-butoxide and dimethyl sulfoxide under visible-light irradiation. Ir(ppy)₃was found to be an effective photoredox catalyst for this reaction. The reactions of aryl iodides occurred at room temperature. Elevated temperature was required for aryl bromides. Homolytic aromatic substitution was proposed to be the operative reaction pathway.

Predicts

1H NMR

13C NMR

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http://pubs.acs.org/doi/10.1021/ol400946k

more info

Shifts

Index	Name	Shift (ppm)
19	H7	6.582
1	H1	7.655
5	H5	7.655
15	H6	6.885
11	H2	7.415
7	H4	7.415
9	H3	7.362
17	H8	7.471

“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