Imine Reduction Using Iron Catalysts

Imine Reduction Using Iron Catalysts

Abnormal-NHC-Fe(0) complex outperforms noble metal catalysts


Read more

http://www.chemistryviews.org/details/news/9749451/Imine_Reduction_Using_Iron_Catalysts.html?elq_mid=11741&elq_cid=1558306

A Highly Efficient Base-Metal Catalyst: Chemoselective Reduction of Imines to Amines Using An Abnormal-NHC–Fe(0) Complex

Mrinal Bhunia†, Pradip Kumar Hota†, Gonela Vijaykumar†, Debashis Adhikari‡, and Swadhin K. Mandal*†

† Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, India

‡ Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, SAS Nagar 140306, India

Organometallics, Article ASAP

DOI: 10.1021/acs.organomet.6b00478

P

*E-mail for S.K.M.: swadhin.mandal@iiserkol.ac.in.

http://pubs.acs.org/doi/abs/10.1021/acs.organomet.6b00478

A base-metal, Fe(0)-catalyzed hydrosilylation of imines to obtain amines is reported here which outperforms its noble-metal congeners with the highest TON of 17000. The catalyst, (aNHC)Fe(CO)4, works under very mild conditions, with extremely low catalyst loading (down to 0.005 mol %), and exhibits excellent chemoselectivity. The facile nature of the imine reduction under mild conditions has been further demonstrated by reducing imines towards expensive commercial amines and biologically important N-alkylated sugars, which are difficult to achieve otherwise. A mechanistic pathway and the source of chemoselectivity for imine hydrosilylation have been proposed on the basis of the well-defined catalyst and isolable intermediates along the catalytic cycle.



Swadhin K. Mandal

Swadhin Mandal Associate Professor Dept: Chemical Sciences (DCS) E-mail: swadhin.mandal [at] iiserkol.ac.in Personal homepage: Click Here

Research Interest: 

Organometallic chemistry and its application in catalysis, new drug development and material chemistry

Academic Background:

1. BSc (Chemistry), University of Kalyani, 1993, Secured 3rd Rank in University
2. MSc (Chemistry), University of Kalyani, 1996, Secured first rank in University
3. PhD (Chemistry), Indian Institute of Science Bangalore, 2002

Positions:

1. Postdoctoral Fellow, University of California, Riverside (2002 - 2005)
2. Alexander von Humboldt Fellow, University of Goettingen (2006 - 2007)
3. Assistant Professor, IISER Kolkata (2007 - 2013)
4. Associate Professor, IISER Kolkata (2013 - 2014)
5. Associate Professor, IISER Kolkata ( - )

Awards and Honors:

1. Alexander von Humboldt Fellowship from Alexander von Humboldt Foundation (2005)
2. YIM Boston Young Scientist Award from YIM Boston at MIT, USA (2012)

Selected Publications
    

• Bhunia et al. Organometallics, in press, 2016. ​
• Paira, Singh et al. J. Org. Chem., 2016, 81 (6), 2432-2441.

• Pariyar et al.  J. Am. Chem. Soc. 2015, 137, 5955-5960 (This work was highlighted by Press coverage, see some links  natureINDIA, Business Standard, IBN7, The Statesman,ZeeNews, Yahoo, Crazyengineers, Delhi Daily News, India Samvad, Kansas City Post,Indianapolis Post,  Toronto Telegraph, Seattle India, Maine Mirror, Hawaii Telegraph,Indusage).
• Hota et al. Adv. Synth. Cat. 2015, 357, 3162 - 3170.
• Raha Roy et al.  ACS Catalysis 2014, 4, 4307–4319 (Selected as a significant recent publicationin a cross-journal virtual issue designed to showcase the significant recent publications among ACS Catalysis, Journal of the American Chemical Society, Journal of Organic Chemistry, and Organic Letters.)
• Raha Roy et al.  J. Org. Chem. 2014, 79, 9150-9160. 
•  Sau et al.  Chem. Asian J 2014, 9, 2806-2813. 
• Raman et al. Nature , 2013., 493, 509-513 ( This work was selected for Press Release coverage by Nature, see some links Telegraph, Deccan Herald, Nature India, please see Press Release for more news coverage on this work for further details)
• Santra et al. ACS Catalysis  2013, 3, 2776−2789.
• Mukherjee et al. Organometallics  2013, 32, 7213-7224
• Sau et al. Adv. Synth. Cat.  2013, 355, 2982-2991
• Mukherjee et al. Scientific Reports  2013, 3, 2821.
• Mukherjee et al. Chem. Eur. J. 2012, 18, 10530-10545 (Highlighted with  Frontispiece Graphics)
• Sen et al. Chem. Eur. J. 2012, 18, 54-58.
• Sau et al. Chem. Commun. 2012, 48, 555-557.
• Santra et al. Green Chem. 2011, 13, 3238 – 3247.
• Sen et al. Chem. Commun. 2011, 47, 11972–11974
• Mukherjee et al. Angew. Chem. Int. Ed. 2011, 50, 3968–3972  (Hot Paper)

Professional Recognitions

• "SKM delivers Physics Colloquium at University of Greifswald, Germany", 2016.
• Selected  and presented work as one of the six speakers in “Organometallics Fellowship Symposium” organized at San Francisco during 10-14th August, USA by the ACS Journal Organometallics.
• Joined Editorial Advisory Board of the Journal 'Organometallics' published by American Chemical Society 2013-2015
• Recipient of YIM-Young Scientist Award -2012 by YIM-Boston held during 6-8th October, 2012 at MIT, Boston, USA for his contribution in the area of Organometallic Chemistry. He is one of the two recipients of this award for the year 2012.
• Alexander von Humboldt Fellowship during 2006-2007 at University of Goettingen, Germany.

Selected Publications:

1. Raman, Karthik V; Kamerbeek, Alexander M.; Mukherjee, Arup; Atodiresei, Nicolae; Sen, Tamal K; Lazic, Predrag; Caciuc, Vasile; Michel, Reent; Stalke, Dietmar; Mandal, Swadhin K; Bluegel, Stephan; Muenzenberg, Markus and Moodera, Jagadeesh. 2013. "Interface-engineered templates for molecular spin memory devices." Nature, 493, 509-513
2. Sen, Tamal K; Mukherjee, Arup; Modak, Arghya; Mandal, Swadhin K and Koley, Debasis. 2013. "Substitution Effect on Phenalenyl Backbone in the Rate of Organozinc Catalyzed ROP of Cyclic Esters." Dalton Trans., 42, 1893-1904
3. Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr.; Samuel, Prinson P.; Schulzke, Carola and Mandal, Swadhin K. 2012. "Phenalenyl-Based Organozinc Catalysts for Intramolecular Hydroamination Reactions: A Combined Catalytic, Kinetic, and Mechanistic Investigation of the Catalytic Cycle." Chemistry -A European Journal, 18, 10530-545

Gonela Vijay Kumar, SRF
Research Interest:
Development of Nucleophilic Boron Compounds and its Reactivity.
Email - gonela.vijaykumar@gmail.com

Pradip Kumar Hota, SRF
Research Interest:
Transition Metal Mediated  C-C Coupling Reactions.
Email - pradip.hota87@gmail.com

Mrinal Bhunia, SRF
Research Interest:
Development of Abnormal Carbene based Transition Metal Complexes for Synthesis of Pharmaceutically Important Molecules.
Email - mrinalbhuniaa@gmail.com

Directed Route to Biaryls

Directed Route to Biaryls

Palladium(II)-catalyzed C–H arylation of aromatic alcohols directed by quinolinyl acetal


Read more


http://www.chemistryviews.org/details/ezine/9692891/Directed_Route_to_Biaryls.html?elq_mid=11741&elq_cid=1558306

1. Previous article in issue: The Synthesis of trans-Flavan-3-ol Gallates by Regioselective Oxidative Etherification and Their Cytotoxicity Mediated by 67 LR
2. Next article in issue: Visible-Light-Induced Trifluoromethylation of Isonitrile-Substituted Methylenecyclopropanes: Facile Access to 6-(Trifluoromethyl)-7,8-Dihydrobenzo[k]phenanthridine Derivatives

View issue TOC
Volume 22, Issue 37
September 5, 2016
Pages 13054–13058

Palladium(II)-Catalyzed ortho-Arylation of Aromatic Alcohols with a Readily Attachable and Cleavable Molecular Scaffold

• emferr@uga.edu
1. Department of Chemistry, University of Georgia, Athens, GA, USA
• DOI: 10.1002/chem.201602844

Authors

hemiacetal 9 (0.811 g, Rf = 0.21 in 1:1 hexanes/EtOAc) as yellow solid. (Total amount: 6.87 g, 92% yield over 3 steps). Hemiacetal 9 (characterized as a 100:3 mixture of hemiacetal/aldehyde): 

1 H NMR (400 MHz, DMSOd6) δ 8.31 (s, 1H), 8.06 (d, J = 8.5 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.81-7.72 (m, 1H), 7.66-7.58 (m, 1H), 7.09 (d, J = 7.6 Hz, 1H), 6.27 (d, J = 7.6 Hz, 1H), 5.25 (d, J = 13.6 Hz, 1H), 5.10 (dd, J = 13.6, 1.0 Hz, 1H); 

13C NMR (100 MHz, DMSO-d6) δ 161.5, 147.7, 130.6, 129.3, 128.9, 128.2, 127.4, 126.7, 97.9, 68.3; IR (film) 3194, 1504, 1020, 910, 754 cm-1 ;

 HRMS (ESI+) m/z calc’d for (M + H)+ [C11H9NO2 + H]+ : 188.0706, found 188.0706.

Contact Information:

Associate Professor of Chemistry
University of Georgia
Chemistry Department
Athens, GA 30602
Tel. (706) 542-4231
emferr@uga.edu

CV

As an undergraduate student at Massachusetts Institute of Technology  (1996-2000), Eric worked on copper-catalyzed conjugate reduction chemistry under the direction of Professor Stephen Buchwald.  His Ph.D. research with Professor Brian Stoltz at the California Institute of Technology (2000-2005) focused on the development of synthetically useful novel oxidation systems using palladium catalysis.  Upon completion, he then continued his studies as an American Cancer Society postdoctoral associate at Stanford (2005-2008) with Prof. Barry Trost, where his studies concerned the use of ruthenium and palladium catalyzed cycloisomerizations for the formation of polycyclic compounds.  He then began his independent career as an assistant professor at Colorado State University in 2008. Eric is currently an Associate Professor of Chemistry at the University of Georgia in Athens, GA.

Dr. Qiankun Li

Ph.D., Zhejiang University

Project: Photocatalysis of earth-abundant metals

/////////

Orthogonally Reacting Boron Coupling Reagents: A Novel Multicomponent-Multicatalytic Reaction [(MC)2R] of Dichlorovinylpyrazine

Orthogonally Reacting Boron Coupling Reagents: A Novel Multicomponent-Multicatalytic Reaction [(MC)2R] of Dichlorovinylpyrazine Jordan M. Rebelo, Steffen Kress, Adam, A. Friedman and Mark Lautens Synthesis 2016, ASAP, ASAP-ASAP. DOI: 10.1055/s-0035-1561670 . Mark Lautens , O.C. University Professor J. Bryan Jones Distinguished Professor AstraZeneca Professor of Organic Chemistry NSERC/Merck-Frosst Industrial Research Chair Department of Chemistry Davenport Chemical Laboratories 80 St. George St. University of Toronto Toronto, Ontario M5S 3H6 Tel: (416) 978-6083 Fax: (416) 946-8185 E-Mail: mlautens@chem.utoronto.ca /////////////

SYNTHESIS Highlight

Image by Steven V. Ley and co-workers Augmented Reality: New perspectives for the visualization of molecules This SYNTHESIS paper highlights the combination of enabling technologies to improve the stereoselectivity of a Wolff–Staudinger cascade reaction. Read Article  ›

Synthesis
DOI: 10.1055/s-0035-1562579

paper

© Georg Thieme Verlag Stuttgart · New York

Combination of Enabling Technologies to Improve and Describe the Stereoselectivity of Wolff–Staudinger Cascade Reaction

B. Musioa, F. Mariania, b, E. P. Śliwińskia, M. A. Kabeshova, H. Odajimac, S. V. Ley*a

• aUniversity of Cambridge, Department of Chemistry, Lensfield Road, Cambridge, CB2 1EW, UK   Email:svl1000@cam.ac.uk
• bUniversitat de Barcelona, Laboratori de Química Orgànica, Facultat de Farmàcia, Av. Joan XXIII s/n, 08028 Barcelona, Spain
• cSaida FDS, 143-10 Itsushiki, Yaizu-shi, Shizuoka Prefecture 4250054, Japan

https://www.thieme-connect.de/products/ejournals/html/10.1055/s-0035-1562579?update=true

Abstract

A new, single-mode bench-top resonator was evaluated for the microwave-assisted flow generation of primary ketenes by thermal decomposition of α-diazoketones at high temperature. A number of amides and β-lactams were obtained by ketene generation in situ and reaction with amines and imines, respectively, in good to excellent yields. The preferential formation of trans-configured β-lactams was observed during the [2+2] Staudinger cycloaddition of a range of ketenes with different imines under controlled reaction conditions. Some insights into the mechanism of this reaction at high temperature are reported, and a new web-based molecular viewer, which takes advantage from Augmented Reality (AR) technology, is also described for a faster interpretation of computed data.

N-Benzyl-2-[4-(trifluoromethyl)phenyl]acetamide (4a)

Yield: 65%; white solid; mp 134–136 °C.

1H NMR (600 MHz, CDCl3): δ = 7.61 (d, J = 8.05 Hz, 2 H), 7.41 (d, J = 8.00 Hz, 2 H), 7.32 (d, J = 7.53 Hz, 2 H), 7.28–7.34 (m overlapping d at 7.32 ppm, 1 H), 7.22 (d, J = 7.13 Hz, 2 H), 5.89 (br. s, 1 H), 4.43 (d, J = 5.8 Hz, 2 H), 3.64 (s, 2 H).

13C NMR (150.0 MHz, CDCl3): δ = 169.7, 138.8 (br s), 137.8, 129.6, 129.59 (q, J C–F = 32.5 Hz), 128.7, 127.62, 127.59, 125.8 (q, J C–F = 3.8 Hz), 124.0 (q, J C–F = 272.0 Hz), 43.8, 43.3.

IR (neat): 3238, 3063, 1625, 1556, 1328, 1122, 1070, 753, 698 cm–1.

HRMS: m/z [M + H]+ calcd for C15H15F3NO: 294.1100; found: 294.1090.

/////////////////

The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?

A key pharmaceutical intermediate (1) for production of edivoxetine·HCl was prepared in >99% ee via a continuous Barbier reaction, which improves the greenness of the process relative to a traditional Grignard batch process. The Barbier flow process was run optimally by Eli Lilly and Company in a series of continuous stirred tank reactors (CSTR) where residence times, solventcomposition, stoichiometry, and operations temperature were optimized to produce 12 g h⁻¹crude ketone 6 with 98% ee and 88% in situ yield for 47 hours total flow time. Continuous salt formation and isolation of intermediate 1 from the ketone solution was demonstrated at 89% yield, >99% purity, and 22 g h⁻¹ production rates using MSMPRs in series for 18 hours total flow time. Key benefits to this continuous approach include greater than 30% reduced process mass intensity and magnesium usage relative to a traditional batch process. In addition, the flow process imparts significant process safety benefits for Barbier/Grignard processes including >100× less excess magnesium to quench, >100× less diisobutylaluminum hydride to initiate, and in this system, maximum long-term scale is expected to be 50 L which replaces 4000–6000 L batch reactors.

A continuous flow Barbier reaction was employed for the production of a key pharmaceutical intermediate (1) in the synthesis of edivoxetine·HCl (a highly selective norepinephrine re-uptake inhibitor).
US scientists from Eli Lilly and Company and D&M Continuous Solutions, led by Michael Kopach, report the development of a continuous Barbier reaction which preserves chirality and the product obtained in >99% ee.  The team ran the process in a series of continuous stirred tank reactors, where residence time, solvent composition, stoichiometry and operations temperature were optimised to produce 12 g per hour of the ketone precursor to 1 with 98% ee and 88% in situ yield for 47 hours total flow time.  Continuous salt formation and isolation of 1 could then be achieved from the ketone solution with >99% purity.
This process offers up several significant advantages over a traditional Grignard batch process.  This continuous flow method gave greater than 30% reduced process mass intensity and magnesium usage relative to the batch method.  Equally, the flow process resulted in >100 x less excess magnesium to quench and >100 x less diisobutylaluminum hydride to initiate giving significant safety benefits.  The authors expect that the maximum long-term scale of the process is 50 L which would replace 4000-6000 L batch reactors.

Continuous Flow Barbier Reaction

Figure 2. Continuous Barbier Laboratory Setup

For 100 years, Grignard reactions have been one of the most powerful and effi cient organic chemistry methodologies for C-C bond formation. However, Grignard reactions are also among the most challenging reactions from both operational and potential safety issues due to initiation diffi culties and runaway potential. A close variation to the Grignard reaction is the Barbier reaction wherein the Grignard reagent is prepared in the presence of an electrophile resulting in the immediate consumption of the Grignard. A Barbier reaction using a CSTR was developed for a key pharmaceutical intermediate in production of edivoxetine·HCl (Scheme 4) [9]. In the fl ow setup (Figure 2), solid magnesium is sequestered in the fi rst tank where the Grignard initiation event takes place. CSTR 2 was used as an aging tank and CSTR 3 was the quench tank. CSTRs were used for Grignard reaction rather than a PFDR because of the solid Mg reagent.

Scheme 4: Barbier Reaction to form Ketone 15

Continuous reaction improved process safety, product quality, and process greenness. The continuous reaction achieved >99% ee in situ versus 95% ee batch because of immediate conversion of unstable intermediate. Solvent volumes were reduced 30%. The safety hazards were reduced by decreasing the reactor size by 50X, which reduced chemical potential and also increased heat transfer surface area per unit volume by 4X. DIBAL-H initiating agent was reduced by more than 100X, and excess Mg that must be quenched at the end of reaction was almost eliminated. When run continuously, the commercial scale Grignard formation reactor was expected to be 50L, which replaces 4000-6000L batch reactor.

The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?

Michael E. Kopach,*^a   Dilwyn J. Roberts,^a   Martin D. Johnson,^a  Jennifer McClary Groh,^a   Jonathan J. Adler,^b   John P. Schafer,^b  Michael E. Kobierski^a and   William G. Trankle^a  

 

*Corresponding authors

^aChemical Product Research and Development, Eli Lilly and Company, Indianapolis, USA
E-mail: kopach_michael@lilly.com

^bD&M Continuous Solutions, Indianapolis, USA

Green Chem., 2012,14, 1524-1536

DOI: 10.1039/C2GC35050E

http://pubs.rsc.org/en/Content/ArticleLanding/2012/GC/C2GC35050E#!divAbstract

Three vessel Grignard CSTR process train.

Grignard synthesis of compound 1.


Retrosynthesis of edivoxetine·HCl.
Flow diagram for the whole continuous process from amide 3 to product 1.


Continuous crystallization of compound 1.

Distillation and continuous crystallization of compound 1.

Entry, Rxn temp. (°C), Vol. ratio THF–toluene (%), Conversion (%), ee (%)
//////////The continuous flow,  Barbier reaction,  improved environmental alternative,  Grignard reaction, FLOW SYNTHESIS