Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals

The hypervalent iodine-mediated formation of steroidal 5/5-spiroiminals and 5/5-spiroaminals from steroidal amines is presented. Under the influence of excess PhI(OAc)<sub>2</sub> and iodine in acetonitrile at 0 °C, steroidal amines smoothly underwent cyclization to give a mixture of 5/5...

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Main Authors: Rayala Naveen Kumar, Seongmin Lee
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/29/23/5812
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author Rayala Naveen Kumar
Seongmin Lee
author_facet Rayala Naveen Kumar
Seongmin Lee
author_sort Rayala Naveen Kumar
collection DOAJ
description The hypervalent iodine-mediated formation of steroidal 5/5-spiroiminals and 5/5-spiroaminals from steroidal amines is presented. Under the influence of excess PhI(OAc)<sub>2</sub> and iodine in acetonitrile at 0 °C, steroidal amines smoothly underwent cyclization to give a mixture of 5/5-spiroiminals and 5/5-spiroaminals. This reaction represents the first example of a C-H-activation-mediated formation of a spiroiminal. Presumably, the formation of 5/5-spiroiminals occurs through aminyl radical-mediated cyclization followed by amine-to-imine oxidation.
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spelling doaj-art-bea00211b2774b5b8f9cd4bf0e6dc00c2025-08-20T02:38:39ZengMDPI AGMolecules1420-30492024-12-012923581210.3390/molecules29235812Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-SpiroiminalsRayala Naveen Kumar0Seongmin Lee1The Division of Chemical Biology and Medicinal Chemistry, College of Pharmacy, University of Texas at Austin, Austin, TX 78712, USAThe Division of Chemical Biology and Medicinal Chemistry, College of Pharmacy, University of Texas at Austin, Austin, TX 78712, USAThe hypervalent iodine-mediated formation of steroidal 5/5-spiroiminals and 5/5-spiroaminals from steroidal amines is presented. Under the influence of excess PhI(OAc)<sub>2</sub> and iodine in acetonitrile at 0 °C, steroidal amines smoothly underwent cyclization to give a mixture of 5/5-spiroiminals and 5/5-spiroaminals. This reaction represents the first example of a C-H-activation-mediated formation of a spiroiminal. Presumably, the formation of 5/5-spiroiminals occurs through aminyl radical-mediated cyclization followed by amine-to-imine oxidation.https://www.mdpi.com/1420-3049/29/23/5812hypervalent iodinespiroiminalC-H activationSteroids
spellingShingle Rayala Naveen Kumar
Seongmin Lee
Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
Molecules
hypervalent iodine
spiroiminal
C-H activation
Steroids
title Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
title_full Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
title_fullStr Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
title_full_unstemmed Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
title_short Hypervalent Iodine-Mediated Synthesis of Steroidal 5/5-Spiroiminals
title_sort hypervalent iodine mediated synthesis of steroidal 5 5 spiroiminals
topic hypervalent iodine
spiroiminal
C-H activation
Steroids
url https://www.mdpi.com/1420-3049/29/23/5812
work_keys_str_mv AT rayalanaveenkumar hypervalentiodinemediatedsynthesisofsteroidal55spiroiminals
AT seongminlee hypervalentiodinemediatedsynthesisofsteroidal55spiroiminals