Dihydrooxazine Byproduct of a McMurry–Melton Reaction en Route to a Synthetic Bacteriochlorin

Tran, Vy-Phuong; Matsumoto, Nobuyuki; Nalaoh, Phattananawee; Jing, Haoyu; Chen, Chih-Yuan; Lindsey, Jonathan S.

doi:10.3390/org3030019

Dihydrooxazine Byproduct of a McMurry–Melton Reaction en Route to a Synthetic Bacteriochlorin

Journal Article · Mon Aug 08 00:00:00 EDT 2022 · Organics

DOI:https://doi.org/10.3390/org3030019· OSTI ID:1880405

Tran, Vy-Phuong; Matsumoto, Nobuyuki; ; Jing, Haoyu; Chen, Chih-Yuan;

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.

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15661

OSTI ID:: 1880405

Journal Information:: Organics, Journal Name: Organics Journal Issue: 3 Vol. 3; ISSN ORGAG5; ISSN 2673-401X

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Country unknown/Code not available

Language:: English

References (31)

Synthesis of β-Trifluoromethylated Δ1-Pyrrolines Marrec, Olivier; Christophe, Carole; Billard, Thierry Advanced Synthesis & Catalysis, Vol. 352, Issue 16 https://doi.org/10.1002/adsc.201000487	journal	September 2010
The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation Ballini, Roberto; Petrini, Marino Advanced Synthesis & Catalysis, Vol. 357, Issue 11 https://doi.org/10.1002/adsc.201500008	journal	July 2015
Discovery of the Michael Reaction Tokoroyama, Takashi European Journal of Organic Chemistry, Vol. 2010, Issue 10 https://doi.org/10.1002/ejoc.200901130	journal	February 2010
The Henry reaction: recent examples Luzzio, Frederick A. Tetrahedron, Vol. 57, Issue 6 https://doi.org/10.1016/S0040-4020(00)00965-0	journal	February 2001
A new and simple synthesis of the pyrrole ring system from Michael acceptors and tosylmethylisocyanides van Leusen, A. M.; Siderius, H.; Hoogenboom, B. E. Tetrahedron Letters, Vol. 13, Issue 52 https://doi.org/10.1016/S0040-4039(01)85244-8	journal	January 1972
Recent synthetic developments in the nitro to carbonyl conversion (Nef reaction) Ballini, Roberto; Petrini, Marino Tetrahedron, Vol. 60, Issue 5 https://doi.org/10.1016/j.tet.2003.11.016	journal	January 2004
Synthesis of hydrodipyrrins tailored for reactivity at the 1- and 9-positions Kim, Han-Je; Dogutan, Dilek Kiper; Ptaszek, Marcin Tetrahedron, Vol. 63, Issue 1 https://doi.org/10.1016/j.tet.2006.10.027	journal	January 2007
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 Tabolin, Andrey A.; Lesiv, Alexey V.; Khomutova, Yulia A. Tetrahedron, Vol. 65, Issue 23 https://doi.org/10.1016/j.tet.2009.03.082	journal	June 2009
De Novo Synthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World Lindsey, Jonathan S. Chemical Reviews, Vol. 115, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00065	journal	June 2015
Syntheses and Properties of Metalated Tetradehydrocorrins Sun, Rui; Liu, Mengran; Wang, Pengzhi Inorganic Chemistry, Vol. 61, Issue 31 https://doi.org/10.1021/acs.inorgchem.2c01642	journal	July 2022
Construction of Saturated Oxazolo[3,2- b ][1,2]oxazines via Tandem [3+2]-Cycloaddition/[1,3]-Rearrangement of Cyclic Nitronates and Ketenes Malykhin, Roman S.; Golovanov, Ivan S.; Nelyubina, Yulia V. The Journal of Organic Chemistry, Vol. 86, Issue 23 https://doi.org/10.1021/acs.joc.1c01744	journal	November 2021
Carbonyl-coupling reactions using low-valent titanium McMurry, John E. Chemical Reviews, Vol. 89, Issue 7 https://doi.org/10.1021/cr00097a007	journal	November 1989
The NEF Reaction Noland, Wayland E. Chemical Reviews, Vol. 55, Issue 1 https://doi.org/10.1021/cr50001a003	journal	February 1955
New method for the reductive coupling of carbonyls to olefins. Synthesis of .beta.-carotene McMurry, John E.; Fleming, Michael P. Journal of the American Chemical Society, Vol. 96, Issue 14 https://doi.org/10.1021/ja00821a076	journal	July 1974
New method for the conversion of nitro groups into carbonyls McMurry, John E.; Melton, Jack The Journal of Organic Chemistry, Vol. 38, Issue 26 https://doi.org/10.1021/jo00965a004	journal	December 1973
De Novo Synthesis of Stable Tetrahydroporphyrinic Macrocycles: Bacteriochlorins and a Tetradehydrocorrin Kim, Han-Je; Lindsey, Jonathan S. The Journal of Organic Chemistry, Vol. 70, Issue 14 https://doi.org/10.1021/jo050467y	journal	July 2005
A trans-AB-Bacteriochlorin Building Block Mass, Olga; Lindsey, Jonathan S. The Journal of Organic Chemistry, Vol. 76, Issue 22, p. 9478-9487 https://doi.org/10.1021/jo201967k	journal	November 2011
Synthesis of 24 Bacteriochlorin Isotopologues, Each Containing a Symmetrical Pair of ¹³ C or ¹⁵ N Atoms in the Inner Core of the Macrocycle Chen, Chih-Yuan; Bocian, David F.; Lindsey, Jonathan S. The Journal of Organic Chemistry, Vol. 79, Issue 3 https://doi.org/10.1021/jo402488n	journal	January 2014
Expanded Scope of Synthetic Bacteriochlorins via Improved Acid Catalysis Conditions and Diverse Dihydrodipyrrin-Acetals Krayer, Michael; Ptaszek, Marcin; Kim, Han-Je The Journal of Organic Chemistry, Vol. 75, Issue 4, p. 1016-1039 https://doi.org/10.1021/jo9025572	journal	February 2010
Rational Synthesis of Meso-Substituted Chlorin Building Blocks Strachan, Jon-Paul; O'Shea, Donal F.; Balasubramanian, Thiagarajan The Journal of Organic Chemistry, Vol. 65, Issue 10 https://doi.org/10.1021/jo991942t	journal	May 2000
Swallowtail Bacteriochlorins. Lipophilic Absorbers for the Near-Infrared Borbas, K. Eszter; Lindsey, Jonathan S. Organic Letters, Vol. 10, Issue 10 https://doi.org/10.1021/ol800436u	journal	May 2008
Synthesis and photophysical characteristics of 2,3,12,13-tetraalkylbacteriochlorins Zhang, Shaofei; Kim, Han-Je; Tang, Qun New Journal of Chemistry, Vol. 40, Issue 7 https://doi.org/10.1039/C6NJ00517A	journal	January 2016
Annulated bacteriochlorins for near-infrared photophysical studies Fujita, Hikaru; Jing, Haoyu; Krayer, Michael New Journal of Chemistry, Vol. 43, Issue 19 https://doi.org/10.1039/C9NJ01113G	journal	January 2019
Synthesis of bacteriochlorins bearing diverse β-substituents Jing, Haoyu; Wang, Pengzhi; Chen, Boyang New Journal of Chemistry https://doi.org/10.1039/D1NJ05852E	journal	January 2022
Synthetic studies relevant to biosynthetic research on vitamin B ₁₂ . Part 7. Synthesis of (±)-bonellin dimethyl ester Battersby, Alan R.; Dutton, Christopher J.; Fookes, Christopher J. R. J. Chem. Soc., Perkin Trans. 1, Issue 6 https://doi.org/10.1039/P19880001569	journal	January 1988
Accessing the near-infrared spectral region with stable, synthetic, wavelength-tunable bacteriochlorins Taniguchi, Masahiko; Cramer, David L.; Bhise, Anil D. New Journal of Chemistry, Vol. 32, Issue 6 https://doi.org/10.1039/b717803d	journal	January 2008
Facile synthesis of a B,D-tetradehydrocorrin and rearrangement to bacteriochlorins Aravindu, Kunche; Krayer, Michael; Kim, Han-Je New Journal of Chemistry, Vol. 35, Issue 7 https://doi.org/10.1039/c1nj20027e	journal	January 2011
Synthesis of the isobacteriochlorin macrocycle: a photochemical approach Harrison, Peter J.; Fookes, Christopher J. R.; Battersby, Alan R. Journal of the Chemical Society, Chemical Communications, Issue 15 https://doi.org/10.1039/c39810000797	journal	January 1981
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 Tabolin, Andrey; Lesiv, Alexey; Khomutova, Yulia Synthesis, Vol. 44, Issue 12 https://doi.org/10.1055/s-0031-1290973	journal	May 2012
Recent Advances in the Synthesis and Chemistry of Nitronates Tabolin, Andrey; Sukhorukov, Alexey; Ioffe, Sema Synthesis, Vol. 49, Issue 15 https://doi.org/10.1055/s-0036-1589063	journal	July 2017
Synthesis of Multi-Substituted Pyrrole Derivatives Through [3+2] Cycloaddition with Tosylmethyl Isocyanides (TosMICs) and Electron-Deficient Compounds Ma, Zhengning; Ma, Zicheng; Zhang, Dawei Molecules, Vol. 23, Issue 10 https://doi.org/10.3390/molecules23102666	journal	October 2018

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