An Alternative Approach to the Hydrated Imidazoline Ring Expansion (HIRE) of Diarene-Fused [1.4]Oxazepines

2020 ◽  
Author(s):  
Sergey Grintsevich ◽  
Alexander Sapegin ◽  
Elena Reutskaya ◽  
Stefan Peintner ◽  
Máté Erdélyi ◽  
...  
Keyword(s):  
Ring Expansion ◽  
Alternative Approach ◽  
Imidazoline Ring

scholarly journals Front Cover: An Alternative Approach to the Hydrated Imidazoline Ring Expansion (HIRE) of Diarene‐Fused [1.4]Oxazepines (Eur. J. Org. Chem. 35/2020)

2020 ◽  
Vol 2020 (35) ◽  
pp. 5635-5635
Author(s):  
Sergey Grintsevich ◽  
Alexander Sapegin ◽  
Elena Reutskaya ◽  
Stefan Peintner ◽  
Máté Erdélyi ◽  
...  
Keyword(s):  
Ring Expansion ◽  
Front Cover ◽  
Alternative Approach ◽  
Imidazoline Ring

Rare Medium-Sized Rings Prepared via Hydrolytic Imidazoline Ring Expansion (HIRE)

2018 ◽  
Vol 83 (17) ◽  
pp. 9707-9717 ◽  
Author(s):  
Angelina Osipyan ◽  
Alexander Sapegin ◽  
Alexander S. Novikov ◽  
Mikhail Krasavin
Keyword(s):  
Ring Expansion ◽  
Imidazoline Ring

scholarly journals Synthesis of Highly Functionalised Furo[3,4-b]pyrans: Towards the Fungal Metabolite (−)-TAN-2483B

2021 ◽  
Author(s):  
◽  
R.M. Kalpani K. Somarathne
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Cyclopropane Ring ◽  
Ring Expansion ◽  
Ethyl Esters ◽  
Pyran Ring ◽  
Synthetic Strategy ◽  
Alternative Approach ◽  
Synthetic Approaches

<p>Carbohydrate-derived cyclopropanes combine both the stereochemical wealth of carbohydrates and the reactivity of cyclopropanes. A diverse variety of reaction modes for these cyclopropyl carbohydrates can be harnessed for the synthesis of natural products and other targets.  The natural products (−)-TAN-2483A and (−)-TAN-2483B are fungal secondary metabolites displaying a variety of bioactivities such as inhibition of c-src kinase action and parathyroid hormone-induced bone resorption. This thesis described several synthetic approaches to the natural product (−)-TAN-2483B and analogues of (−)-TAN-2483B employing cyclopropane ring expansion.  The synthetic route to (−)-TAN-2483B began with the readily available substrate D-mannose. The pyran ring unsaturation of the natural product was established by a cyclopropanation-ring expansion sequence. A synthetic strategy via dichlorocyclopropane-based intermediates is described in chapter 2. This being unsuccessful, an alternative approach via 2-fomyl-glycal was developed in chapter 3. The chapter 2 and 3 provided a solid background for the achievement of the analogues synthesis illustrated in chapter 4 via dibromocyclopropane. Lewis acid-mediated alkynylation followed by Pdcatalysed carbonylative lactonisation was successfully utilised in the revelation of the furo[3,4-b]pyran ring skeleton. This route afforded analogues of TAN-2483B; the Z-and E-unsaturated ethyl esters 140 and 141 and hydroxy(−)-TAN-2483B 145. The total synthesis of (−)-TAN-2483B was not achieved due to unforeseen obstacles encountered in the deoxygenation of the side arm of 335 (Chapter 4) into the E-propenyl side arm of (−)-TAN-2483B.</p>

An attempt at the hydrated imidazoline ring expansion (HIRE) of diarene-fused [1,4]diazepinones delivers selective dopamine D2 receptor ligands

Synthesis ◽  
2021 ◽  
Author(s):  
Sergey Grintsevich ◽  
Alexander V. Sapegin ◽  
Andrzej Bojarski ◽  
Beata Duszyńska ◽  
Mikhail Krasavin
Keyword(s):  
Dopamine D2 Receptor ◽  
D2 Receptor ◽  
Ring Expansion ◽  
Side Chain ◽  
Receptor Ligands ◽  
Structure Activity Relationships ◽  
Dopamine D2 ◽  
Structure Activity ◽  
Imidazoline Ring ◽  
Selective Dopamine

Attempts to extend the hydrated imidazoline ring expansion (HIRE) strategy to a series of diarene-fused [1,4]diazepinones (earlier applied successfully to bis-pyrido substrate nevirapine) resulted in no ring expansion but rather 2-aminoethyl side chain expulsion. This seeming setback (setting the limitations to the HIRE methodology substrate scope) led to the discovery of selective dopamine D2 ligands with elements of structure-activity relationships.

Zooming in on the hydrated imidazoline ring expansion: Factors influencing the rate of N → N′ aroyl migration in N-aroyl-N-(hetero)aryl ethylenediamines

2020 ◽  
Vol 61 (42) ◽  
pp. 152423
Author(s):  
Kseniya Lavit ◽  
Elena Reutskaya ◽  
Sergey Grintsevich ◽  
Alexander Sapegin ◽  
Mikhail Krasavin
Keyword(s):  
Ring Expansion ◽  
Factors Influencing ◽  
Imidazoline Ring

scholarly journals Structurally diverse arene-fused ten-membered lactams accessed via hydrolytic imidazoline ring expansion

2017 ◽  
Vol 15 (14) ◽  
pp. 2906-2909 ◽  
Author(s):  
Alexander Sapegin ◽  
Angelina Osipyan ◽  
Mikhail Krasavin
Keyword(s):  
Medicinal Chemistry ◽  
Ring Expansion ◽  
Membered Ring ◽  
Synthetic Methods ◽  
Ring Systems ◽  
New Hire ◽  
Imidazoline Ring

A facile approach to hitherto unknown ten-membered ring systems via a hydrolytic imidazoline ring expansion (HIRE) is described. Medium-sized rings are scarce in the contemporary medicinal chemistry toolbox. The new HIRE strategy broadens the arsenal of synthetic methods to obtain such scaffolds.

Rethinking Hydrolytic Imidazoline Ring Expansion: A Common Approach to the Preparation of Medium-Sized Rings via Side-Chain Insertion into [1.4]Oxa- and [1.4]Thiazepinone Scaffolds

2018 ◽  
Vol 84 (4) ◽  
pp. 1693-1705 ◽  
Author(s):  
Elena Reutskaya ◽  
Angelina Osipyan ◽  
Alexander Sapegin ◽  
Alexander S. Novikov ◽  
Mikhail Krasavin
Keyword(s):  
Ring Expansion ◽  
Side Chain ◽  
Imidazoline Ring

scholarly journals Synthesis of Highly Functionalised Furo[3,4-b]pyrans: Towards the Fungal Metabolite (−)-TAN-2483B

2021 ◽  
Author(s):  
◽  
R.M. Kalpani K. Somarathne
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Natural Product ◽  
Cyclopropane Ring ◽  
Ring Expansion ◽  
Ethyl Esters ◽  
Pyran Ring ◽  
Synthetic Strategy ◽  
Alternative Approach ◽  
Synthetic Approaches

<p>Carbohydrate-derived cyclopropanes combine both the stereochemical wealth of carbohydrates and the reactivity of cyclopropanes. A diverse variety of reaction modes for these cyclopropyl carbohydrates can be harnessed for the synthesis of natural products and other targets.  The natural products (−)-TAN-2483A and (−)-TAN-2483B are fungal secondary metabolites displaying a variety of bioactivities such as inhibition of c-src kinase action and parathyroid hormone-induced bone resorption. This thesis described several synthetic approaches to the natural product (−)-TAN-2483B and analogues of (−)-TAN-2483B employing cyclopropane ring expansion.  The synthetic route to (−)-TAN-2483B began with the readily available substrate D-mannose. The pyran ring unsaturation of the natural product was established by a cyclopropanation-ring expansion sequence. A synthetic strategy via dichlorocyclopropane-based intermediates is described in chapter 2. This being unsuccessful, an alternative approach via 2-fomyl-glycal was developed in chapter 3. The chapter 2 and 3 provided a solid background for the achievement of the analogues synthesis illustrated in chapter 4 via dibromocyclopropane. Lewis acid-mediated alkynylation followed by Pdcatalysed carbonylative lactonisation was successfully utilised in the revelation of the furo[3,4-b]pyran ring skeleton. This route afforded analogues of TAN-2483B; the Z-and E-unsaturated ethyl esters 140 and 141 and hydroxy(−)-TAN-2483B 145. The total synthesis of (−)-TAN-2483B was not achieved due to unforeseen obstacles encountered in the deoxygenation of the side arm of 335 (Chapter 4) into the E-propenyl side arm of (−)-TAN-2483B.</p>

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