Divergent Cascade Ring Expansion Reactions of Acryloyl Imides

Gideon James Grogan; Will Orukotan; Kleopas Palate; Balazs Pogranyi; Ryan Epton; Lee Duff; A.C. Whitwood; Jason Martin Lynam; William Paul Unsworth; Philipp Bobinski

doi:10.1002/chem.202303270

Divergent Cascade Ring Expansion Reactions of Acryloyl Imides

Gideon James Grogan, Will Orukotan, Kleopas Palate, Balazs Pogranyi, Ryan Epton, Lee Duff, A.C. Whitwood, Jason Martin Lynam, William Paul Unsworth, Philipp Bobinski

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Macrocyclic and medium-sized ring ketones, lactones and
lactams can all be made from common acryloyl imide starting
materials via divergent, one-pot cascade ring expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII) catalysed dihydoxylation, rearrangement via a 4-atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ring
expansion. In the dihydroxylation series, 3- or 4-atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control.

Original language	English
Article number	e202303270
Journal	Chemistry : A European Journal
DOIs	https://doi.org/10.1002/chem.202303270
Publication status	Accepted/In press - 21 Nov 2023

Access to Document

10.1002/chem.202303270Licence: CC BY

Accepted_ManuscriptAccepted author manuscript, 1.04 MBLicence: CC BY

Cite this

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title = "Divergent Cascade Ring Expansion Reactions of Acryloyl Imides",

abstract = "Macrocyclic and medium-sized ring ketones, lactones andlactams can all be made from common acryloyl imide startingmaterials via divergent, one-pot cascade ring expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII) catalysed dihydoxylation, rearrangement via a 4-atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ringexpansion. In the dihydroxylation series, 3- or 4-atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control.",

author = "Grogan, {Gideon James} and Will Orukotan and Kleopas Palate and Balazs Pogranyi and Ryan Epton and Lee Duff and A.C. Whitwood and Lynam, {Jason Martin} and Unsworth, {William Paul} and Philipp Bobinski",

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doi = "10.1002/chem.202303270",

language = "English",

journal = "Chemistry : A European Journal",

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T1 - Divergent Cascade Ring Expansion Reactions of Acryloyl Imides

AU - Grogan, Gideon James

AU - Orukotan, Will

AU - Palate, Kleopas

AU - Pogranyi, Balazs

AU - Epton, Ryan

AU - Duff, Lee

AU - Whitwood, A.C.

AU - Lynam, Jason Martin

AU - Unsworth, William Paul

AU - Bobinski, Philipp

PY - 2023/11/21

Y1 - 2023/11/21

N2 - Macrocyclic and medium-sized ring ketones, lactones andlactams can all be made from common acryloyl imide startingmaterials via divergent, one-pot cascade ring expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII) catalysed dihydoxylation, rearrangement via a 4-atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ringexpansion. In the dihydroxylation series, 3- or 4-atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control.

AB - Macrocyclic and medium-sized ring ketones, lactones andlactams can all be made from common acryloyl imide startingmaterials via divergent, one-pot cascade ring expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII) catalysed dihydoxylation, rearrangement via a 4-atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ringexpansion. In the dihydroxylation series, 3- or 4-atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control.

U2 - 10.1002/chem.202303270

DO - 10.1002/chem.202303270

M3 - Article

SN - 0947-6539

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

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