Record-Breaking Steric Crowding in Trialkylamines Prepared by Oxidative Ring Opening

Dedicated to Professor Harald Günther on the occasion of his 85^th birthday

Abstract

Epoxidation of olefinic heterocyclic amines and subsequent acid-catalyzed hydrolysis or alternatively the direct dihydroxylation with the help of osmium tetroxide led to diols, which underwent ring cleavage in the presence of lead tetraacetate to give 3-isopropyl-2,2,4,4-tetramethyl-3-azahexanedial and 3-tert-butyl-2,2,4,4-tetramethyl-3-azapentanedial. Whereas the former dialdehyde is a highly unstable model compound because of a rapid intramolecular aldol reaction, the latter product proves to be isolable at room temperature. Furthermore, this compound is the first open-chain tri-tert-alkylamine establishing in a new record of steric crowding in tertiary amines. Strong tendencies to a Hofmann-like elimination reaction or to ring-closing reactions were observed when the aldehyde units of 3-tert-butyl-2,2,4,4-tetramethyl-3-azapentanedial were transformed into other functionalities, since both types of reactions led to a significantly decrease of the steric stress.

Key words

amines - nitrogen heterocycles - olefin oxidation - ring cleavage - steric hindrance

Publikationsverlauf

Eingereicht: 01. Juli 2020

Angenommen nach Revision: 04. August 2020

Artikel online veröffentlicht:
05. Oktober 2020

• References

• 1 Substitution on the Amine Nitrogen, Science of Synthesis, Vol. 40a. Enders D. Thieme; Stuttgart: 2008
• 2a Kampmann D, Stuhlmüller G, Simon R, Cottet F, Leroux F, Schlosser M. Synthesis 2005; 1028
• 2b Dagonneau M, Kagan ES, Mikhailov VI, Rozantsev EG, Sholle VD. Synthesis 1984; 895
• 3 Hünig S, Kiessel M. Chem. Ber. 1958; 91: 380
• 4 Barriga S. Synlett 2001; 563
• 5a Stone TJ, Buckman T, Nordio PL, McConnell HM. Proc. Natl. Acad. Sci. U.S.A. 1965; 54: 1010
• 5b Keana JF. W. Chem. Rev. 1978; 78: 37
• 6a Step EN, Turro NJ, Gande ME, Klemchuk PP. Macromolecules 1994; 27: 2529
• 6b Dagonneau M, Ivanov VB, Rozantsev EG, Sholle VD, Kagan ES. J. Macromol. Sci., Polym. Rev. 1982; 22: 169
• 6c Kurumada T, Ohsawa H, Fujita T, Toda T, Yoshioka T. J. Polym. Sci., Polym. Chem. 1985; 23: 1477
• 7 Iashin V, Chernichenko K, Pápai I, Repo T. Angew. Chem. Int. Ed. 2016; 55: 14146
• 8a Hiltmann R, Wollweber H, Wirth W, Gösswald R. Angew. Chem. 1960; 72: 1001
• 8b Kürti L. Science 2015; 348: 863
• 9a Sartori G, Savage DW. Ind. Eng. Chem. Fundam. 1983; 22: 239
• 9b Hook RJ. Ind. Eng. Chem. Res. 1997; 36: 1779
• 10a Chaplinski V, de Meijere A. Angew. Chem. Int. Ed. 1996; 35: 413
• 10b Druzhinin SI, Dubbaka SR, Knochel P, Kovalenko SA, Mayer P, Senyushkina T, Zachariasse KA. J. Phys. Chem. A 2008; 112: 2749
• 10c Yang M, Albrecht-Schmitt T, Cammarata V, Livant P, Makhanu DS, Sykora R, Zhu W. J. Org. Chem. 2009; 74: 2671
• 11a March J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure. McGraw-Hill; Tokyo: 1968: 123
• 11b Smith MB. March’s Advanced Organic Chemistry, 7th ed. Wiley; Hoboken: 2013: 206
• 12a Bock H, Göbel I, Havlas Z, Liedle S, Oberhammer H. Angew. Chem. Int. Ed. 1991; 30: 187
• 12b Wong TC, Collazo LR, Guziec FS. Jr. Tetrahedron 1995; 51: 649
• 12c Anderson JE, Casarini D, Lunazzi L. J. Org. Chem. 1996; 61: 1290
• 12d Boese R, Bläser D, Antipin MY, Chaplinski V, de Meijere A. Chem. Commun. 1998; 781
• 13 Banert K, Heck M, Ihle A, Kronawitt J, Pester T, Shoker T. J. Org. Chem. 2018; 83: 5138
• 14 Banert K, Seifert J. Org. Chem. Front. 2019; 6: 3517
• 15 For an alternative synthesis of 17b, see: Zakrzewski J. Synth. Commun. 1988; 18: 2135
• 16 Pauly H. Justus Liebigs Ann. Chem. 1902; 322: 77
• 17a Nazarski R, Skolimowski J, Skowronski R. Pol. J. Chem. 1979; 53: 821
• 17b Cygler M, Dobrynin K, Grabowski MJ, Nazarski R, Skowronski R. J. Chem. Soc., Perkin Trans. 2 1985; 1495
• 18 Bordeaux D, Gagnaire G, Lajzérowicz J, Commandeur G. Acta Crystallogr., Sect. C 1983; 39: 1656