Prof. Carsten Bolm

 

abstract graphic

(R)-(−)-2-[(5-oxido-5-phenyl-5λ4-isoquino[4,3-c][2,1]benzothiazin- 12-yl)amino]benzonitrile (4).

Copper-catalyzed cross-coupling between (S)-S-methyl-S-phenylsulfoximine (1) and 2-iodobenzonitrile (2) resulted in the discovery of an unprecedented one-pot triple arylation sequence to give (R)-(−)-2-[(5-oxido-5-phenyl-5λ4-isoquino[4,3-c][2,1]benzothiazin- 12-yl)amino]benzonitrile (4). Here, we describe the synthesis of the title compound (R)-4 and the elucidation of its structure by means of various techniques.

Carsten Bolm with wife and new baby Lewon, March 2009 (344 / 433)

Germany

Molbank 20142014(3), M834; doi:10.3390/M834

(R)-(−)-2-[(5-Oxido-5-phenyl-5λ4-isoquino[4,3-c][2,1]benzothiazin-12-yl)amino]benzonitrile

* Author to whom correspondence should be addressed; E-Mail: carsten.bolm@oc.rwth-aachen.de;
Fax: +29-241-80-92-391. http://bolm.oc.rwth-aachen.de/

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

 Carsten Bolm

   Dr. rer. nat., Professor of Organic Chemistry
Institut für Organische Chemie
RWTH Aachen University
Landoltweg 1
D-52074 Aachen, Germany
Tel.: + 49 241-80 94 675
FAX : + 49 241-80 92 391
Prof. Carsten Bolm
The combined organic phases were dried with
MgSO4 and filtered. After evaporation of solvents, the oily residue was subjected to column
chromatography (SiO2, n-pentane/EtOAc = 2/1). Product (R)-4 was isolated as a yellow solid.
Additionally, sulfoximine (S)-3 was separately obtained as a yellow oil (61% yield, 0.899 g, 3.51 mmol).
Yield: 23% (0.616 g, 1.34 mmol); mp = 211–212 °C (racemate: 263–265 °C); [α] = −57.7 (c = 0.6 g,
100 mL−1, CHCl3); 1H NMR (600 MHz, CDCl3): δ = 7.11 (ddd, J = 8.2 Hz, 7.1 Hz, 1.2 Hz, 1H, Ar-H),
7.25 (dd, J = 8.0 Hz, 1.1 Hz, 1H, Ar-H), 7.27 (td, J = 7.6 Hz, 1.0 Hz, 1H, Ar-H), 7.42–7.50 (m, 3H,
Ar-H), 7.50–7.58 (m, 3H, Ar-H), 7.70 (dd, J = 7.8 Hz, 1.5 Hz, 1H, Ar-H), 7.78 (ddd, J = 8.8 Hz, 7.5
Hz, 1.6 Hz, 1H, Ar-H), 7.87–7.90 (m, 2H, Ar-H), 8.07 (dd, J = 7.6 Hz, 1.6 Hz, 1H, Ar-H), 8.19–8.24
(m, 2H, Ar-H and NH), 8.50 (dd, J = 8.1 Hz, 1.5 Hz, 1H, Ar-H), 8.81 (d, J = 8.4 Hz, 1H, Ar-H) ppm;
13C NMR (150 MHz, CDCl3): δ = 103.4 (C), 105.5 (Ar-C), 116.9 (Ar-C), 117.5 (C), 118.4 (Ar-C),
120.3 (Ar-CH), 121.8 (Ar-CH), 122.3 (Ar-CH), 123.6 (Ar-CH), 123.8 (Ar-CH), 124.8 (Ar-CH), 125.9
(Ar-CH), 127.6 (Ar-CH), 127.7 (2 Ar-CH), 129.0 (2 Ar-CH), 132.0 (2 Ar-CH), 132.4 (Ar-CH), 132.5
(Ar-C), 132.8 (Ar-CH), 133.9 (Ar-CH), 141.7 (Ar-C), 144.0 (Ar-C), 144.2 (Ar-C), 148.0 (C), 153.2
(C) ppm; 1
H NMR [600 MHz, (CD3)2SO]: δ = 6.98 (ddd, J = 8.2 Hz, 7.2 Hz, 1.1 Hz, 1H, Ar-H), 7.11
(dd, J = 8.1 Hz, 0.8 Hz, 1H, Ar-H), 7.40 (ddd, J = 8.6 Hz, 7.2 Hz, 1.6 Hz, 1H, Ar-H), 7.53 (td, J = 7.7 Hz,
1.0 Hz, 1H, Ar-H), 7.56–7.60 (m, 2H, Ar-H), 7.60–7.64 (m, 1H, Ar-H), 7.67–7.73 (m, 2H, Ar-H), 7.80
(d, J = 8.0 Hz, 1H, Ar-H), 7.84–7.88 (m, 3H, Ar-H), 8.04 (dd, J = 7.8 Hz, 1.4 Hz, 1H, Ar-H), 8.12 (dd,
J = 7.7 Hz, 1.8 Hz, 1H, Ar-H), 8.18 (dd, J = 8.1 Hz, 1.5 Hz, 1H, Ar-H), 8.68 (dd, J = 7.5 Hz, 1.7 Hz,
1H, Ar-H), 10.51 (s, 1H, NH) ppm;
13C NMR [150 MHz, (CD3)2SO]: δ = 103.5 (C), 110.2 (Ar-C),
117.0 (Ar-C), 117.4 (C), 118.0 (Ar-C), 119.7 (Ar-CH), 122.6 (Ar-CH), 123.6 (Ar-CH), 124.5 (Ar-CH),
125.6 (Ar-CH), 126.2 (Ar-CH), 127.1 (2 Ar-CH), 127.3 (Ar-CH), 127.4 (Ar-CH), 129.3 (2 Ar-CH),
131.7 (Ar-C), 131.8 (Ar-CH), 132.2 (Ar-CH), 133.0 (Ar-CH), 133.1 (Ar-CH), 133.9 (Ar-CH), 141.9
(Ar-C), 143.7 (Ar-C), 144.0 (Ar-C), 147.4 (C), 155.6 (C) ppm;
IR (ATR): ν = 3640, 3258, 2324, 2221,
2020, 1980, 1936, 1601, 1572, 1546, 1515, 1484, 1459, 1422, 1376, 1333, 1277, 1241, 1206, 1149,
1092, 1038, 1009, 976, 844, 794, 754, 720, 681 cm−1; EI-MS: m/z (%) = 458 (100) [M]+, 410 (15), 381(22), 357 (9), 333 (62), 102 (6), 77 (12), 51 (10); CI-MS: m/z (%) = 499 (3) [M+C3H5]+, 487 (16)[M+C2H5]+
, 459 (100) [M+H]+, 358 (7); ESI-MS: m/z (%) = 939 (9) [2M+Na]+, 497 (8) [M+K]+, 481(24) [M+Na]+, 459 (42) [M+H]+, 358 (100); ESI-HRMS: m/z calcd for C28H19N4OS: 459.12741; found
459.12793 with ∆ = 1.14 ppm; anal. calcd for C28H18N4OS (458.54): C, 73.34; H, 3.96; N, 12.22;
found C, 73.44; H, 4.09; N, 12.30; HPLC: tr = 16.8 min [major], tr = 25.2 min [minor] (Chiralpak AD-H,
0.6 mL min−1, n-heptane/isopropanol = 60/40, λ = 230 nm, 20 °C); >99% ee.
Crystallographic data were collected with a Bruker Kappa APEX II CCD-diffractometer with
monochromatic Mo–Kα radiation (λ = 0.71073 Å) and a CCD detector. The structure was solved by
direct methods using SHELXS-97 and refined against F2 on all data by full-matrix least-squares
methods using SHELXL-97 [13,14].
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

Prof. Carsten Bolm
Carsten Bolm was born in Braunschweig in 1960. He studied chemistry at the TU Braunschweig (Germany) and at the University of Wisconsin, Madison (USA). In 1987 he obtained his doctorate with Professor Reetz in Marburg (Germany). After postdoctoral training with Professor Sharpless at MIT, Cambridge (USA), Carsten Bolm worked in Basel (Switzerland) with Professor Giese to obtain his habilitation. In 1993 he became Professor of Organic Chemistry at the University of Marburg (Germany), and since 1996 he has a chair of Organic Chemistry at the RWTH Aachen (Germany).

GERMANY….

Dr. Swamy Sreenivasa……..Department of Chemistry, Tumkur University

Dr. Swamy Sreenivasa……..Department of Chemistry, Tumkur University

Dr. Swamy Sreenivasa……..Department of Chemistry, Tumkur University, India

abstract graphic

N-(2-Chloro-5-cyanophenyl)-4,4,4-trifluorobutanamide (3) was synthesized by reacting 4,4,4-trifluorobutanoic acid (1) with 2-amino-4-chlorobenzonitrile (2) in the presence of triethylamine and propylphosphonic anhydride in ethyl acetate. Character­ization of the compound was done by IR, 1H-NMR, 13C-NMR, LC-MS and CHN analysis.

Molbank 20132013(3), M803; doi:10.3390/M803
Short Note

N-(2-Chloro-5-cyanophenyl)-4,4,4-trifluorobutanamide

Dr. S. Sreenivasa 
Associate Professor,                        Tumkur University
email………..drsreenivasa@yahoo.co.in. 
1 Center for Advanced Materials, Department of Chemistry, Tumkur University, Tumkur-572103, India2 Tadimety Aromatics Pvt. Ltd, Hirehalli Industrial Area, Tumkur-572168, India
* Author to whom correspondence should be addressed.
Synthesis of N-(2-Chloro-5-cyanophenyl)-4,4,4-trifluorobutanamide (3)
compound (3) as a colorless solid with Rf = 0.79.
Yield: 1.63 g (90%).
Melting point: 151–153 °C.
MS: m/z = 277.64 (M++1).
IR: νmax/cm−1: 3340 (N-H), 2228 (CN), 1698 (CO), 1342–1140 (CF3 streching).
1H-NMR (DMSO-d6) δ: 10.47 (s, 1H, NH), 7.88 (d, J = 8.7 Hz, 1H, Ar-H), 7.80 (d, J = 1.9 Hz, 1H,
Ar-H), 7.45 (dd, J = 8.3 Hz and J = 1.5 Hz, 1H, Ar-H), 2.74 (t, J = 7.5 Hz, 2H, COCH2),
2.67–2.55 (m, 2H, CF3CH2).
13C-NMR (DMSO-d6) δ: 169.3, 141.2, 138.3, 134.8, 128.7 CF3, 125.9, 124.6, 115.9, 104.9, 28.7, 27.8.
Elemental analysis: Calculated for C11H8ClF3N2O: C, 47.76%; H, 2.91%; N, 10.13%. Found: C,
47.79%; H, 2.96%; N, 10.19%.

Center for Advanced Materials, Department of Chemistry, Tumkur University, Tumkur-572103, India
kote-anjeneya-swami-statue-in-tumkur
Aralaguppe, Tumkur
The elevated highway between Nelamangala and Yeshwanthpur junction on Tumkur Road, National
Cuisine of Tumkur

http://www.tumakuruonline.in/city-guide/cuisine-of-tumkur

Food preparation for my marriage (Tumkur Ameen) Tags: food india nature landscape wildlife environment karnataka ahmed kunigal traditionalfood ameen tumkur ddhills hebburElephant on the street (Tumkur Ameen) Tags: india elephant nature forest landscape nationalpark wildlife western environment karnataka mammals ahmed coorg kabini begur ghats nilgiris kunigal wildlifesanctuary ameen kodagu bandipur bisle tumkur nagarahole talakaveri kakanakote makutta karapura antharasanthe antarasanthe hediyala hghills brahmagiris ddhills hebbur elephantbathingFood preparation for my marriage (Tumkur Ameen) Tags: food india nature environment karnataka mammals ahmed kunigal traditionalfood ameen tumkur hghills ddhills hebbur

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http://flickrhivemind.net/Tags/ddhills/Interesting

Benne Idli Sagu at Pavithra Idli Hotel, Kyathasandra Tumkur

http://blog.kudugal.org/2011/09/second-storm-aka-whirlwind-2-day-1.html

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Regioselective Rapid Synthesis of Fully-substituted 1,2,3-Triazoles Mediated by Propargyl Cations

Regioselective Rapid Synthesis of Fully-substituted 1,2,3-Triazoles Mediated by Propargyl Cations
Huan Zhang, Hiroki Tanimoto, Tsumoru Morimoto, Yasuhiro Nishiyama, Kiyomi Kakiuchi
Org. Lett. 2013, 15, 5222-5225.

http://pubs.acs.org/doi/abs/10.1021/ol402387w

Regioselective rapid triazole syntheses at low temperature are described. Organic azides and propargyl cations generated by acids gave fully substituted 1H-1,2,3-triazoles. Most reactions could be performed in 5 min at not only rt but also −90 °C. Both terminal and internal alkynes were acceptable, and the sterically bulky substituents could afford the products smoothly. Various types of three-component coupling reactions were demonstrated, and the presence of allenylaminodiazonium intermediates was indicated.

PAINS filters now on mobile, with MolPrime+

Cheminformatics 2.0

molprime_painsOne of the trends that you should expect to see more of from apps produced by Molecular Materials Informatics is a shift toward performing more advanced calculations internally on the mobile device, rather than calling out to a cloud service. One of the recent demonstrations was shown with the Approved Drugs app, which can now call up Bayesian models for various predictions. The next version of MolPrime+ that is awaiting review on the AppStore incorporates internal calculation of log P, and also brings the ability to identify PAINS filters for molecular structures.

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Important Industrial Procedures Revisited in Flow: Very Efficient Oxidation and N-Alkylation Reactions with High Atom-Economy

New Drug Approvals

http://www.akademiai.com/content/u87p126856085276/?p=2f48c96a10a64882aeb5c47c657a10b7&pi=4

JournalJournal of Flow Chemistry
PublisherAkadémiai Kiadó
ISSN2062-249X (Print)
2063-0212 (Online)
SubjectFlow Chemistry
IssueVolume 3, Number 2/June 2013
Pages51-58
DOI10.1556/JFC-D-12-00025
Authors
Gellért Sipos1, Viktor Gyollai1, Tamás Sipőcz1, György Dormán1, László Kocsis1 Email for laszlo.kocsis@thalesnano.com, Richard V. Jones1, Ferenc Darvas1

1ThalesNano Zahony u. 7 1031 Budapest Hungary

Abstract

The atom economy concept is one of the earliest recognition for green and sustainable aspects of organic synthesis. Over the years, novel technologies emerged that made this important feature of reactions into practice. Continuous-flow devices increased the efficiency of the chemical transformations with novel process windows (high T, high p and heterogeneous packed catalysts etc.) and increased safety which turned the attention to reexamine old, industrial processes. Oxidation can be performed under flow catalytic conditions with molecular oxygen; alcohols can be oxidized to…

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Continuous Flow Synthesis of alpha-Halo Ketones: Building Blocks for Anti-retroviral Agents

New Drug Approvals

Chiral alpha-halo ketones derived from N-protected amino acids are key building blocks for the synthesis of HIV protease inhibitors such as atazanavir used in HAART combination therapy.

Kappe and De Souza have reported a continuous flow through route to these intermediates which utilises a tube-in-tube reactor to introduce diazomethane generated on demand into the reaction stream containing mixed anhydride derivatives of N-protected amino acids. The resulting alpha-diazo ketones are then decomposed with HCl or HBr to afford the corresponding alpha-halo ketones.

This process allows the safe generation, separation and use of diazomethane in a continuous integrated multi-step synthesis of important API intermediates.

Abstract Image

The development of a continuous flow process for the multistep synthesis of α-halo ketones starting from N-protected amino acids is described. The obtained α-halo ketones are chiral building blocks for the synthesis of HIV protease inhibitors, such as atazanavir and darunavir. The synthesis starts with…

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The application of flow microreactors to the preparation of a family of casein kinase I inhibitors

New Drug Approvals

Graphical Abstract

The Application of Flow Microreactors to the Preparation of a Family of Casein Kinase I Inhibitors.
Venturoni, F.; Nikbin, N.; Ley S. V.; Baxendale, I. R.
Org. Biomol. Chem.2010, 8, 1798-1806.
Link: 10.1039/b925327kpdf icon

In this article we demonstrate how a combination of enabling technologies such as flow synthesis, solid-supported reagents and scavenging resins utilised under fully automated software control can assist in typical medicinal chemistry programmes. In particular automated continuous flow methods have greatly assisted in the optimisation of reaction conditions and facilitated scale up operations involving hazardous chemical materials. Overall a collection of twenty diverse analogues of a casein kinase I inhibitor has been synthesised by changing three principle binding vectors.

aInnovative Technology Centre, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK

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