Greener Synthesis of Pristane by Flow Dehydrative Hydrogenation of Allylic Alcohol Using a Packed-Bed Reactor Charged by Pd/C As a Single Catalyst

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2021 Oct 13

PMID 34641390

Authors

Takayoshi Kasakado

Yuki Hirobe

Akihiro Furuta

Mamoru Hyodo

Takahide Fukuyama

Ilhyong Ryu

Affiliations

Soon will be listed here.

Abstract

Our previous work established a continuous-flow synthesis of pristane, which is a saturated branched alkane obtained from a Basking Shark. The dehydration of an allylic alcohol that is the key to a tetraene was carried out using a packed-bed reactor charged by an acid-silica catalyst (HO-SAS) and flow hydrogenation using molecular hydrogen via a Pd/C catalyst followed. The present work relies on the additional propensity of Pd/C to serve as an acid catalyst, which allows us to perform a flow synthesis of pristane from the aforementioned key allylic alcohol in the presence of molecular hydrogen using Pd/C as a single catalyst, which is applied to both dehydration and hydrogenation. The present one-column-two-reaction-flow system could eliminate the use of an acid catalyst such as HO-SAS and lead to a significant simplification of the production process.

References

Tanaka K, Motomatsu S, Koyama K, Tanaka S, Fukase K . Large-scale synthesis of immunoactivating natural product, pristane, by continuous microfluidic dehydration as the key step. Org Lett. 2007; 9(2):299-302. DOI: 10.1021/ol062777o. View

Ren W, Sun F, Chu J, Shi Y . A Pd-Catalyzed Site-Controlled Isomerization of Terminal Olefins. Org Lett. 2020; 22(5):1868-1873. DOI: 10.1021/acs.orglett.0c00168. View

Gado K, Silva S, Paloczi K, Domjan G, Falus A . Mouse plasmacytoma: an experimental model of human multiple myeloma. Haematologica. 2001; 86(3):227-36. View

Yu T, Jiao J, Song P, Nie W, Yi C, Zhang Q . Recent Progress in Continuous-Flow Hydrogenation. ChemSusChem. 2020; 13(11):2876-2893. DOI: 10.1002/cssc.202000778. View

Satoh M, Richards H, Shaheen V, Yoshida H, Shaw M, Naim J . Widespread susceptibility among inbred mouse strains to the induction of lupus autoantibodies by pristane. Clin Exp Immunol. 2000; 121(2):399-405. PMC: 1905709. DOI: 10.1046/j.1365-2249.2000.01276.x. View

MATTHEWS L . Reproduction in the basking shark, Cetorhinus maximus (Gunner). Philos Trans R Soc Lond B Biol Sci. 2014; 234(612):247-316. DOI: 10.1098/rstb.1950.0003. View

Maung M, Shon Y . Effects of Noncovalent Interactions on the Catalytic Activity of Unsupported Colloidal Palladium Nanoparticles Stabilized with Thiolate Ligands. J Phys Chem C Nanomater Interfaces. 2018; 121(38):20882-20891. PMC: 5758047. DOI: 10.1021/acs.jpcc.7b07109. View

Holmdahl R, Lorentzen J, Lu S, Olofsson P, Wester L, Holmberg J . Arthritis induced in rats with nonimmunogenic adjuvants as models for rheumatoid arthritis. Immunol Rev. 2002; 184:184-202. DOI: 10.1034/j.1600-065x.2001.1840117.x. View

Irfan M, Glasnov T, Kappe C . Heterogeneous catalytic hydrogenation reactions in continuous-flow reactors. ChemSusChem. 2011; 4(3):300-16. DOI: 10.1002/cssc.201000354. View

10.

Cossar P, Hizartzidis L, Simone M, McCluskey A, Gordon C . The expanding utility of continuous flow hydrogenation. Org Biomol Chem. 2015; 13(26):7119-30. DOI: 10.1039/c5ob01067e. View

11.

Yoswathananont N, Nitta K, Nishiuchi Y, Sato M . Continuous hydrogenation reactions in a tube reactor packed with Pd/C. Chem Commun (Camb). 2004; (1):40-2. DOI: 10.1039/b410014j. View

12.

Larionov E, Lin L, Guenee L, Mazet C . Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols. J Am Chem Soc. 2014; 136(48):16882-94. DOI: 10.1021/ja508736u. View