Dihydrooxazine Byproduct of a McMurry–Melton Reaction en Route to a Synthetic Bacteriochlorin
Vy-Phuong Tran, Nobuyuki Matsumoto, Phattananawee Nalaoh, Haoyu Jing, Chih-Yuan Chen, Jonathan Lindsey
Organics · pp. 262–274 · Published 8 Aug 2022
10.3390/org3030019Abstract
A synthetic route to gem-dimethyl-substituted bacteriochlorins—models of native bacteriochlorophylls—relies on the formation of a dihydrodipyrrin precursor via a series of established reactions: van Leusen pyrrole formation, Vilsmeier formylation, Henry reaction, borohydride reduction, Michael addition, and McMurry–Melton pyrroline formation. The latter is the least known of the series. Here, the McMurry–Melton reaction of a 2-(6-oxo-2-nitrohexyl)pyrrole in the presence of TiCl3 and an ammonium acetate buffer formed the expected Δ1-pyrroline, as well as an unexpected polar, cyclic byproduct (a 5,6-dihydro-4H-1,2-oxazin-6-ol), each attached to the 2-methylpyrrole unit. Both species were characterized by single-crystal X-ray diffraction. The McMurry–Melton reaction is a type of intercepted Nef reaction (the transformation of a nitroalkyl motif into a carbonyl group), where both the Δ1-pyrroline and the dihydrooxazine derive from the reaction of the nitrogen derived from the nitro group upon complete or partial reductive deoxygenation, respectively, with the γ-keto group. The report also considers competing Nef and McMurry–Melton reactions, the nature of available TiCl3 reagents, and the use of ammonium acetate for buffering the TiCl3/HCl reagent.
References (41)
- 1 Grimm, 2006, An Overview of Chlorophylls and Bacteriochlorophylls. Biochemistry, Biophysics, Functions and Applications [DOI]
- 2 Kim, 2005, De Novo Synthesis of Stable Tetrahydroporphyrinic Macrocycles: Bacteriochlorins and a Tetradehydrocorrin [DOI]
- 3 Krayer, 2010, Expanded Scope of Synthetic Bacteriochlorins via Improved Acid Catalysis Conditions and Diverse Dihydrodipyrrin-Acetals [DOI]
- 4 Siderius, 1972, A New and Simple Synthesis of the Pyrrole Ring System from Michael Acceptors and Tosylmethylisocyanides [DOI]
- 5 Ma, Z., Ma, Z., and Zhang, D. (2018). Synthesis of Multi-Substituted Pyrrole Derivatives Through [3 + 2] Cycloaddition with Tosylmethyl Isocyanides (TosMICs) and Electron-Deficient Compounds. Molecules, 23. [DOI]
- 6 Jones, 1997, The Vilsmeier Reaction of Fully Conjugated Carbocycles and Heterocycles
- 7 Luzzio, 2001, The Henry Reaction: Recent Examples [DOI]
- 8 Tokoroyama, T. (2010). Discovery of the Michael Reaction. Eur. J. Org. Chem., 2009–2016. [DOI]
- 9 Mass, 2011, A trans-AB-Bacteriochlorin Building Block [DOI]
- 10 Kobayashi, 2006, Spectroscopy and Structure Determination [DOI]
- 11 Noland, 1955, The Nef Reaction [DOI]
- 12 Wolfrom, 1960, John Ulric Nef 1862–1915 (Biographical Memoir)
- 13 Pinnick, 1990, The Nef Reaction
- 14 Ballini, 2004, Recent Synthetic Developments in the Nitro to Carbonyl Conversion (Nef Reaction) [DOI]
- 15 Ballini, 2015, The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation [DOI]
- 16 McMurry, 1973, A New Method for the Conversion of Nitro Groups into Carbonyls [DOI]
- 17 Lindsey, 2015, De Novo Synthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating our Green World [DOI]
- 18 McMurry, 1989, Carbonyl-Coupling Reactions Using Low-Valent Titanium [DOI]
- 19 McMurry, 1974, A New Method for the Reductive Coupling of Carbonyls to Olefins [DOI]
- 20 Harrison, P.J., Fookes, C.J.R., and Battersby, A.R. (1981). Synthesis of the Isobacteriochlorin Macrocycle: A Photochemical Approach. J. Chem. Soc. Chem. Commun., 797–799. [DOI]
- 21 Battersby, 1988, Synthetic Studies Relevant to Biosynthetic Research on Vitamin B12. Part 7. Synthesis of (±)-Bonellin Dimethyl Ester [DOI]
- 22 Marrec, 2010, Synthesis of β-Trifluoromethylated Δ1-Pyrrolines [DOI]
- 23 Strachan, 2000, Rational Synthesis of Meso-Substituted Chlorin Building Blocks [DOI]
- 24 Kim, 2007, Synthesis of Hydrodipyrrins Tailored for Reactivity at the 1- and 9-Positions [DOI]
- 25 Taniguchi, 2008, Accessing the Near-Infrared Spectral Region with Stable, Synthetic, Wavelength-Tunable Bacteriochlorins [DOI]
- 26 Borbas, 2008, Swallowtail Bacteriochlorins. Lipophilic Absorbers for the Near-Infrared [DOI]
- 27 Aravindu, 2011, Facile Synthesis of a B,D-Tetradehydrocorrin and Rearrangement to Bacteriochlorins [DOI]
- 28 Chen, 2014, Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of 13C or 15N Atoms in the Inner Core of the Macrocycle [DOI]
- 29 Zhang, 2016, Synthesis and Photophysical Characteristics of 2,3,12,13-Tetraalkylbacteriochlorins [DOI]
- 30 Fujita, 2019, Annulated Bacteriochlorins for Near-Infrared Photophysical Studies [DOI]
- 31 Jing, 2022, Synthesis of Bacteriochlorins Bearing Diverse β-Substituents [DOI]
- 32 Sun, R., Liu, M., Wang, P., Qin, Y., Schnedermann, C., Maher, A.G., Zheng, S.-L., Liu, S., Chen, B., and Zhang, S. (2022). Synthesis and Properties of Metalated Tetradehydrocorrins. Inorg. Chem., in press. [DOI]
- 33 Tabolin, 2009, Rearrangement of 3-Alkylidene-2-siloxy-tetrahydro-1,2-oxazines (ASENA). A New Approach Toward the Synthesis of 3-α-Hydroxyalkyl-5, 6-dihydro-4H-1,2-oxazines [DOI]
- 34 Tabolin, 2012, Synthesis of α-Prolinols and 2-Amino-1,5-diols from Primary Nitroalkanes and Other Simple Precursors via Intermediacy of 5,6-Dihydro-4H-1,2-oxazines [DOI]
- 35 Malykhin, 2021, Construction of Saturated Oxazolo[3,2-b]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes [DOI]
- 36 Tabolin, 2017, Recent Advances in the Synthesis and Chemistry of Nitronates [DOI]
- 37 Weast, R.C. (1971–1972). CRC Handbook of Chemistry and Physics, The Chemical Rubber Co.. [52nd ed.].
- 38 (2002). Bruker (2009) APEX2, SAINT and SADABS, Bruker AXS Inc.
- 39 (2022, June 02). Available online: https://onlinelibrary.wiley.com/iucr/doi/10.1107/S2053229614024218.
- 40 (2022, June 02). Available online: http://scripts.iucr.org/cgi-bin/paper?S0021889808042726.
- 41 (2022, June 02). Available online: https://docs.scipy.org/doc/scipy/reference/generated/scipy.optimize.fsolve.html.
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