CuI nanoparticles as recyclable heterogeneous catalysts for C-N bond formation reactions

CuI nanoparticles as recyclable heterogeneous catalysts for C-N bond formation reactions

Catal. Sci. Technol., 2017, 7,2857-2864
DOI: 10.1039/C7CY00832E, Paper

Manoranjan Kumar, Vinod Bhatt, Onkar S. Nayal, Sushila Sharma, Vishal Kumar, Maheshwar S. Thakur, Neeraj Kumar, Rajaram Bal, Bikram Singh, Upendra Sharma
Herein, copper iodide nanoparticles (NPs) are reported for the reductive amination of carbonyl compounds for the first time.

From the journal:

Catalysis Science & Technology

CuI nanoparticles as recyclable heterogeneous catalysts for C–N bond formation reactions

 

Manoranjan Kumar,ab  Vinod Bhatt,ab  Onkar S. Nayal,ab  Sushila Sharma,ab  Vishal Kumar,c Maheshwar S. Thakur,ab  Neeraj Kumar,ab  Rajaram Bal,*d  Bikram Singh*ab  and  Upendra Sharma*ab 

 Author affiliations

*Corresponding authors

aNatural Product Chemistry and Process Development Department, CSIR-Institute of Himalayan Bioresource Technology Palampur, Himachal Pradesh 176 061, India
E-mail: bikramsingh@ihbt.res.in, upendra@ihbt.res.in, upendraihbt@gmail.com

bAcademy of Scientific and Innovative Research, Anusandhan Bhawan, 2 Rafi Marg, New Delhi-110001, India

cState Key Laboratory of Elemento-Organic Chemistry, Nankai University, Weijin Road 300 071, Tianjin, China

dRefining Technology Division, CSIR-Indian Institute of Petrolium, Dehradun, India
E-mail: raja@iip.res.in

Abstract

Herein, copper iodide nanoparticles (NPs) are reported for the reductive amination of carbonyl compounds for the first time. The generated NPs were characterized by TEM, EDX, XRD and XPS analyses. The XRD patterns, XPS, and EDX analysis confirmed that the resulting NPs were CuI instead of Cu. The TEM images of CuI exhibited the size of monodispersed spherical NPs in the range of 4 ± 2 nm. These generated NPs can be used as versatile heterogeneous catalysts for important organic transformations. As a proof of concept, CuI NPs were successfully applied as heterogeneous catalysts for the synthesis of secondary amines, amides and triazoles. CuI NPs can be easily recovered and recycled up to six times.

http://pubs.rsc.org/en/Content/ArticleLanding/2017/CY/C7CY00832E?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2Fcy+%28RSC+-+Catalysis+Science+%26+Technology+latest+articles%29#!divAbstract

.1H and 13C NMR values of synthesized compounds

N‒benzylaniline (3a): Brown oil (168 mg, 92% yield),

1H NMR (CDCl3, 600MHz) δ : 4.35 (s, 2H), 6.66 (d, 2H, J = 7.8 Hz), 6.72 (t, 2H, J =7.32 Hz), 7.18‒7.21 (m, 2H), 7.28 (t, 1H, J = 7.14 Hz), 7.35‒7.40 (m, 4H);

13C NMR (CDCl3, 150 MHz) δ : 48.3, 112.8, 117.6, 127.2, 127.5, 128.6, 129.3, 139.4, 148.1;

HRESIMS calcd for C13H14N [M+H]+ 184.1129, found 184.1109.

1H AND 13C NMR PREDICT

//////////

N-(1-adamantile)-4-chlorobenzamide ( NMR IS EASY)

N-(1-adamantile)-4-chlorobenzamide

EVEN MOM CAN TEACH U NMR

N-(1-Adamantile)-4-chlorobenzamide (7a): White solid (231 mg, 80%),

1H NMR(600 MHz, CDCl3): 7.71 (d, J = 8.22 Hz, 2H), 7.41 (d, J = 8.22 Hz, 2H), 6.36 (brs, 1H), 4.24 (d, J = 7.02 Hz, 1H), 2.04 (s, 2H), 1.90 (brs, 6H), 1.84 (d, J = 13.08 Hz, 2H), 1.78 (s, 2H), 1.71 (d, J = 12.84 Hz, 2H);

13C NMR(150 MHz, CDCl3): 165.5, 137.4, 133.7, 128.8, 128.2, 53.8, 37.4, 37.1, 32.1, 31.9, 27.2, 27.1.

HRESIMS calcd for C17H21ClNO [M+H]+ 290.1312, found 290.1301.

1H AND 13C NMR PREDICT

///////http://www.rsc.org/suppdata/c7/cy/c7cy00832e/c7cy00832e1.pdf

N‒(4’‒methoxyCinnamyl)aniline ( NMR IS EASY)

N‒(4’‒methoxyCinnamyl)aniline

N‒(4'‒Methoxycinnamyl)aniline (3s): Yellow brown solid (203 mg, 85% yield),

mp. 75 oC,

1H NMR (CDCl3, 600 MHz): δ 3.86 (s, 3H), 3.94 (d, 2H, J = 11.5 Hz), 6.20‒ 6.29 (m, 1H), 6.60 (d, 1H, J = 15.9 Hz), 6.74 (d, 2H, J = 8.28 Hz), 6.80 (t, 1H, J = 6.9 Hz), 6.93 (d, 2H, J = 4.32 Hz), 7.24‒7.29 (m, 2H), 7.38 (d, 2H, J = 8.6 Hz);

13C NMR (CDCl3, 150 MHz): δ 46.7, 55.7, 113.5, 114.4, 117.9, 125.2, 127.9, 129.7, 130.1, 131.5, 148.6, 159.6;

HRESIMS calcd for C16H18NO [M+H]+ 240.1388, found 240.1378.

EVEN MOM CAN TEACH U NMR

//////////

3-Phenylpropionic acid

3-Phenylpropionic acid (2z) 1

1) Jiang, X.; Zhang, J.; Ma. S. J. Am. Chem. Soc. 2016, 138, 8344

Yield: 94% (142 mg), white solid. Melting point: 47-49 °C (lit.18 49 °C)

(18) Helavi, V. B.; Solabannavar, S. B.; Desai, U. V.; Mane, R. B. J. Chem. Research 2003, 3, 174.

1 H NMR (400 MHz, CDCl3) δ 7.34 – 7.17 (m, 5H), 2.97 (t, J = 7.8 Hz, 2H), 2.69 (t, J = 7.8 Hz, 2H).

13C NMR (101 MHz, CDCl3) δ 179.82, 140.28, 128.71, 128.41, 126.52, 35.64, 30.73

1H AND 13C NMR PREDICT

Aerobic Oxidation of Diverse Primary Alcohols to Carboxylic Acids with a Heterogeneous Pd–Bi–Te/C (PBT/C) Catalyst

Maaz S. Ahmed†, David S. Mannel‡, Thatcher W. Root‡ , and Shannon S. Stahl*† 

†Department of Chemistry and ‡Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00223

 

*E-mail: stahl@chem.wisc.edu.

Maaz Ahmed

PhD Candidate in the Stahl Lab at University of Wisconsin-Madison

Prof. Shannon S. Stahl

Department of Chemistry
University of Wisconsin-Madison
1101 University Avenue
Madison , Wisconsin 53706
Tel: (608) 265-6288
Fax: (608) 262-6143
stahl@chem.wisc.edu
Room 6132a Chemistry

Abstract

Heterogeneous catalytic aerobic oxidation methods represent a near-ideal approach for the conversion of primary alcohols to carboxylic acids. Here, we report that a heterogeneous catalyst composed of Pd, Bi, and Te supported on activated carbon is highly effective for the oxidation of diverse benzylic and aliphatic primary alcohols, including 5-(hydroxymethyl)furfural (HMF) and substrates bearing heterocycles and other important functional groups. In many cases, the desired carboxylic acid product is obtained in >90% yield. Additionally, the catalyst has been demonstrated in a continuous-flow packed-bed reactor for the oxidation of benzyl alcohol, achieving near-quantitative yield while undergoing over 30 000 turnovers.

http://pubs.acs.org/doi/suppl/10.1021/acs.oprd.7b00223/suppl_file/op7b00223_si_001.pdf

DATA FROM OTHER SOURCES.........

Experiments:

1. 1D-1H: Peaks_list 2. 2D-[1H,1H]-TOCSY: 3. 1D-13C: Peaks_list 4. 1D-13C DEPT90: Peaks_list 5. 1D-13C DEPT135: Peaks_list 6. 2D-[1H,13C]-HSQC: Peaks_list 7. 2D-[1H,13C]-HMBC: 8. 2D-[1H,1H]-COSY:

///////////

syn-3,5-Dihydroxy Hexanoate

pure 8 (2.4 g, HPLC purity, 92%). [α]D25 = −41.3 (c = 1.0, CHCl3), >99.5% de.(8g, 9) 1H NMR (CDCl3, 400 MHz), δ/ppm: 1.47 (s, 9H), 1.71–1.75 (m, 2H), 2.42–2.44 (m, 2H), 2.54–2.56 (m, 2H), 3.71 (brs, 2H), 4.18–4.22 (m, 1H), 4.26–4.31 (m, 1H).

t-butyl 6-cyano-(5R)-hydroxy-3-oxo-hexanoate

t-Butyl-6-cyano-(3R,5R)-dihydroxyhexanoate is an advanced chiral precursor for the synthesis of the side chain pharmacophore of cholesterol-lowering drug atorvastatin. Herein, a robust carbonyl reductase (LbCR) was newly identified from Lactobacillus brevis, which displays high activity and excellent diastereoselectivity toward bulky t-butyl 6-cyano-(5R)-hydroxy-3-oxo-hexanoate (7). The engineered Escherichia coli cells harboring LbCR and glucose dehydrogenase (for cofactor regeneration) were employed as biocatalysts for the asymmetric reduction of substrate 7. As a result, as much as 300 g L–1 of water-insoluble substrate was completely converted to the corresponding chiral diol with >99.5% de in a space–time yield of 351 g L–1 d–1, indicating a great potential of LbCR for practical synthesis of the very bulky and bi-chiral 3,5-dihydroxy carboxylate side chain of best-selling statin drugs.

Identification of a Robust Carbonyl Reductase for Diastereoselectively Building syn-3,5-Dihydroxy Hexanoate: a Bulky Side Chain of Atorvastatin

Xu-Min Gong† , Gao-Wei Zheng*† , You-Yan Liu‡§, and Jian-He Xu*†

† State Key Laboratory of Bioreactor Engineering, Shanghai Collaborative Innovation Center for Biomanufacturing, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China

‡ School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, P. R. China

§ Guangxi Key Laboratory of Biorefinery, Guangxi Academy of Sciences, Nanning 530003, Guangxi, P. R. China

Org. Process Res. Dev., Article ASAP

DOI: 10.1021/acs.oprd.7b00194

 

*E-mail: gaoweizheng@ecust.edu.cn; fax: (+86)-21-64250840., *E-mail: jianhexu@ecust.edu.cn; fax: (+86)-21-64252498.