A solvent-free catalytic protocol for the Achmatowicz rearrangement

Abstract

Reported here is the development of an environmentally friendly catalytic (KBr/oxone) and solvent-free protocol for the Achmatowicz rearrangement (AchR). Different from all previous methods is that the use of chromatographic alumina (Al₂O₃) allows AchR to proceed smoothly in the absence of any organic solvent and therefore considerably facilitates the subsequent workup and purification with minimal environmental impacts. Importantly, this protocol allows for scaling up (from milligram to gram), recycling of the Al₂O₃, and integrating with other reactions in a one-pot sequential manner.

A solvent-free catalytic protocol for the

Achmatowicz rearrangement

Guodong Zhao^a  and  Rongbiao Tong*^ab 

 Author affiliations

*Corresponding authors

^aDepartment of Chemistry, The Hong Kong University of Science and Technology, Clearwater Bay, Kowloon, China
E-mail: rtong@ust.hk
Fax: +(852)23581594
Tel: +(852) 23587357

^bHKUST Shenzhen Research Institute, Shenzhen 518057, China

https://pubs.rsc.org/en/Content/ArticleLanding/2019/GC/C8GC03030H?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

1n: colorless oil, 0.33 g, 73% yield for 2 steps.

1H-NMR (400 MHz, DMSO) δ: 7.59–7.58 (m, 1H), 7.45 (s, 2H), 6.40 (dd, J = 3.2, 1.8 Hz, 1H), 6.29 (d, J = 3.2 Hz, 1H), 5.49 (s, 1H), 4.74–4.60 (m, 1H), 4.18–4.07 (m, 2H), 2.09–2.04 (m, 2H).

13C-NMR (100 MHz, DMSO) δ: 157.6, 142.4, 110.7, 106.1, 66.5, 62.8, 35.2. IR (KBr) 3282.9, 2928.7, 1627.4, 1562.5, 1353.8, 1174.6, 1074.0, 999.7, 918.4, 742.8 cm-1 ;

HRMS (CI+ ) (m/z) calcd. for C7H11NO5S [M]+ 221.0352; found 221.0354.

  

2n (EtOAc/hexane = 3:1):colorless oil (dr 7:3), 46 mg, 97%.

1H-NMR (400 MHz, DMSO) δ: 7.48–7.47 (m, 2H), 7.34–7.02 (m, 2H), 6.12–6.03 (m, 1H), 5.61–5.48 (m, 1H), 4.60 (dd, J = 8.3, 4.1 Hz, 0.7H), 4.28 (ddd, J = 8.8, 4.0, 1.3 Hz, 0.3H), 4.20–4.11 (m, 2H), 2.27–2.20 (m, 1H), 1.97–1.86 (m, 1H).

13C-NMR (100 MHz, DMSO) δ: 196.7, 196.5, 151.9, 148.3, 127.7, 126.0, 90.9, 87.2, 74.6, 70.1, 65.8, 65.8, 30.3, 29.6. IR (KBr) 3370.4, 2987.0, 1689.5, 1364.3, 1268.0, 1178.4, 1023.3, 928.3, 755.1 cm-1 ;

HRMS (CI+ ) (m/z) calcd. for C7H11NO6S [M]+ 237.0302; found 237.0315.

 

////////////////Achmatowicz rearrangement

Synthesis of β-keto sulfones via a multicomponent reaction through sulfonylation and decarboxylation

1-Phenyl-2-(phenylsulfonyl)ethan-1-one (2a) 1

1H NMR (400 MHz, CDCl3) δ 7.92 (m, 4H), 7.70 – 7.58 (m, 2H), 7.54 (t, J = 7.6 Hz, 2H), 7.48 (t, J = 7.3 Hz, 2H), 4.74 (s, 2H).

13C NMR (101 MHz, CDCl3) δ 187.9, 138.7, 135.7, 134.4, 134.2, 129.3, 129.2, 128.9, 128.6, 63.4.

References 1. Lu, Q.; Zhang, J.; Peng, P.; Zhang, G.; Huang, Z.; Yi, H.; Millercd, T. J.; Lei, A. Chem. Sci. 2015, 6, 4851.

Jiyao Yu,^b  Runyu Mao,^a  Qingyu Wang^a  and  Jie Wu*^ac 

*Corresponding authors

^aDepartment of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China
E-mail: jie_wu@fudan.edu.cn

^bSchool of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive, Atlanta, USA

^cState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

Abstract

A copper(I)-catalyzed synthesis of β-keto sulfones through a multicomponent reaction of aryldiazonium tetrafluoroborates, 3-arylpropiolic acids, sulfur dioxide, and water was developed. This reaction proceeds through a tandem radical process, and the sulfonyl radical, generated from the combination of aryldiazonium tetrafluoroborates with DABCO·(SO₂)₂, acts as the key intermediate. The transformation involves sulfonylation and decarboxylation, which allows for the efficient synthesis of the desired β-keto sulfones.

Nickel-catalyzed carbonylation of arylboronic acids with DMF as a CO source

Bis(4-methoxyphenyl)methanone

bis(4-methoxyphenyl)methanone (3b) The title product was purified by column chromatography and was obtained in 83% yield (110 mg). Rf = 0.3 (petroleum ether/ethyl acetate 30:1), light yellow oil.

1H NMR (400 MHz, CDCl3) δ (ppm):

7.80 (d, J = 8.8 Hz, 2H),  AROM H ORTHO TO -C=0

6.97 (d, J = 8.8 Hz, 2H),  AROM H ORTHO TO -OCH3

3.89 (s, 6H); TWO -OCH3 GPS

13C NMR (100 MHz, CDCl3) δ (ppm): 194.4, 162.9, 132.2, 132.1, 113.4, 55.5;

IR (KBr): 2957, 1671, 1593, 1260, 1093, 806 cm-1; HRMS(ESI) calc. for (M + Na+ ) 265.0844; found 265.0835.

MOM CAN TEACH YOU NMR

Nickel-catalyzed carbonylation of arylboronic acids with DMF as a CO source

Org. Chem. Front., 2017, 4,569-572
DOI: 10.1039/C7QO00001D, Research Article

Yang Li, Dong-Huai Tu, Bo Wang, Ju-You Lu, Yao-Yu Wang, Zhao-Tie Liu, Zhong-Wen Liu, Jian Lu
By using N,N-dimethylformamide (DMF) as a CO source, nickel-catalyzed carbonylation of arylboronic acids was demonstrated as an efficient and facile protocol for the synthesis of diaryl ketones.

Yang Li,^ab  Dong-Huai Tu,^a  Bo Wang,^a  Ju-You Lu,^a  Yao-Yu Wang,^b  Zhao-Tie Liu,*^c  Zhong-Wen Liu^c  and  Jian Lu*^a 

*Corresponding authors

^aState Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an, China
E-mail: lujian204@263.net

^bKey Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, 710069, China

^cKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, China
E-mail: ztliu@snnu.edu.cn

Abstract

By using N,N-dimethylformamide (DMF) as a CO source, the cheap metal nickel-catalyzed carbonylation of arylboronic acids was demonstrated as an efficient and facile protocol for the synthesis of diaryl ketones. Results indicated that NiBr₂·diglyme was the best pre-catalyst among the investigated transitional metal salts, and excellent yields were achieved via C–H and C–N bond cleavage.

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