Synthesis of Imide and Amine Derivatives Via Deoxyamination of Alcohols Using -Haloimides and Triphenylphosphine

Overview

Journal ChemistrySelect

Specialty Chemistry

Date 2023 May 19

PMID 37207246

Authors

Charles D Irving

Jack T Floreancig

Makafui Gasonoo

Alexandra S Kelley

Sebastien Laulhe

Affiliations

Soon will be listed here.

Abstract

A deoxyamination methodology of activated and unactivated alcohols is presented. The reaction is mediated by phosphonium intermediates generated from -haloimides and triphenylphosphine. The protocol allows for the synthesis of phthalimide and amine derivatives in moderate to good yields at room temperature. A series of NMR experiments have provided insight into the reactive intermediates involved and the mechanism of this deoxyamination reaction.

Citing Articles

Synthesis, antioxidant activity, antimicrobial efficacy and molecular docking studies of 4-chloro-2-(1-(4-methoxyphenyl)-4,5-diphenyl-1-imidazol-2-yl)phenol and its transition metal complexes.

Ahmad M, Siddique A, Khalid M, Ali A, Shaheen M, Tahir M RSC Adv. 2023; 13(14):9222-9230.

PMID: 36959880 PMC: 10029809. DOI: 10.1039/d2ra08327b.

References

Laulhe S, Geers T, Shi X, Zhang X, Nantz M . Electron Ionization-Induced Release of Coded Isotopic Reporter Ions in an Zone of Minimal Interference for Quantifiable, Multiplexed GC-MS Analyses. Anal Methods. 2013; 5(18). PMC: 3822575. DOI: 10.1039/C3AY41124A. View

Hodosi G, GALAMBOS G, Podanyi B, Kuszmann J . Synthesis of 7-(2,4-dichlorophenyl)-D-erythro-3-hydroxy-5-heptanolide, 6-(2,4-dichlorophenyl)-D-erythro-2,4-dihydroxyhexane-1-sulfonic acid, and 6-(2,4-dichlorophenyl)-D-erythro-2,4-dihydroxyhexylphosphonic acid. Carbohydr Res. 1992; 225(2):269-78. DOI: 10.1016/s0008-6215(00)90500-7. View

Gasonoo M, Thom Z, Laulhe S . Regioselective α-Amination of Ethers Using Stable N-Chloroimides and Lithium tert-Butoxide. J Org Chem. 2019; 84(13):8710-8716. PMC: 9689168. DOI: 10.1021/acs.joc.9b00824. View

Irving C, Floreancig J, Laulhe S . Amide Synthesis through the In Situ Generation of Chloro- and Imido-Phosphonium Salts. ACS Omega. 2020; 5(25):15734-15745. PMC: 7331200. DOI: 10.1021/acsomega.0c02309. View

Vitaku E, Smith D, Njardarson J . Analysis of the structural diversity, substitution patterns, and frequency of nitrogen heterocycles among U.S. FDA approved pharmaceuticals. J Med Chem. 2014; 57(24):10257-74. DOI: 10.1021/jm501100b. View

Huang F, Xu C, Lu D, Shen D, Li T, Liu F . Pd-PEPPSI-IPent Promoted Deactivated Amination of Aryl Chlorides with Amines under Aerobic Conditions. J Org Chem. 2018; 83(16):9144-9155. DOI: 10.1021/acs.joc.8b01205. View

Lipshutz B, Chung D, Rich B, Corral R . Simplification of the Mitsunobu reaction. Di-p-chlorobenzyl azodicarboxylate: a new azodicarboxylate. Org Lett. 2006; 8(22):5069-72. DOI: 10.1021/ol0618757. View

But T, Toy P . Organocatalytic Mitsunobu reactions. J Am Chem Soc. 2006; 128(30):9636-7. DOI: 10.1021/ja063141v. View

Hirose D, Gazvoda M, Kosmrlj J, Taniguchi T . Systematic Evaluation of 2-Arylazocarboxylates and 2-Arylazocarboxamides as Mitsunobu Reagents. J Org Chem. 2018; 83(8):4712-4729. DOI: 10.1021/acs.joc.8b00486. View

10.

Bosanac T, Wilcox C . A photoactivated precipiton for reagent sequestration in solution-phase synthesis. J Am Chem Soc. 2002; 124(16):4194-5. DOI: 10.1021/ja017577g. View

11.

Chen J, Lin J, Xiao J . Dehydroxylation of alcohols for nucleophilic substitution. Chem Commun (Camb). 2018; 54(51):7034-7037. DOI: 10.1039/c8cc03856b. View

12.

Vine K, Locke J, Ranson M, Benkendorff K, Pyne S, Bremner J . In vitro cytotoxicity evaluation of some substituted isatin derivatives. Bioorg Med Chem. 2006; 15(2):931-8. DOI: 10.1016/j.bmc.2006.10.035. View

13.

Quinn R, Konst Z, Michalak S, Schmidt Y, Szklarski A, Flores A . Site-Selective Aliphatic C-H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide. J Am Chem Soc. 2015; 138(2):696-702. PMC: 5562432. DOI: 10.1021/jacs.5b12308. View

14.

Cui X, Dai X, Deng Y, Shi F . Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia. Chemistry. 2013; 19(11):3665-75. DOI: 10.1002/chem.201203417. View

15.

Barrett A, Roberts R, Schroder J . Impurity annihilation: chromatography-free parallel Mitsunobu reactions. Org Lett. 2000; 2(19):2999-3001. DOI: 10.1021/ol006313g. View

16.

Bergstrom C, Sloan C, Lau W, Smith D, Zheng M, Hansel S . Carbamate-appended N-alkylsulfonamides as inhibitors of gamma-secretase. Bioorg Med Chem Lett. 2008; 18(2):464-8. DOI: 10.1016/j.bmcl.2007.11.102. View

17.

Hortner S, Ritschel T, Stengl B, Kramer C, Schweizer W, Wagner B . Potent inhibitors of tRNA-guanine transglycosylase, an enzyme linked to the pathogenicity of the Shigella bacterium: charge-assisted hydrogen bonding. Angew Chem Int Ed Engl. 2007; 46(43):8266-9. DOI: 10.1002/anie.200702961. View

18.

LAYCOCK G, Shulman A . PARTIAL AGONISTS IN THE CENTRAL NERVOUS SYSTEM. Nature. 1963; 200:849-51. DOI: 10.1038/200849a0. View

19.

OHagan D . Pyrrole, pyrrolidine, pyridine, piperidine and tropane alkaloids. Nat Prod Rep. 2000; 17(5):435-46. DOI: 10.1039/a707613d. View

20.

Huang H, Kang J . Oxidation-Reduction Condensation of Diazaphosphites for Carbon-Heteroatom Bond Formation Based on Mitsunobu Mechanism. Org Lett. 2017; 19(3):544-547. DOI: 10.1021/acs.orglett.6b03709. View