Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

to related objects

Abstract: A highly enantioselective cobalt‐catalyzed semipinacol rearrangement of symmetric α,α‐diarylallylic alcohols is disclosed. A chiral cobalt‐salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical–polar crossover steps. This methodology provides access to enantioenriched α‐aryl ketones through invertive displacement of a cobalt (IV) complex during 1,2‐aryl migration. A combination of readily available reagents, silane and N‐fluoropyridinium oxidant, are used to confer this type of reactivity. An exploration into the effect of aryl substitution revealed the reaction tolerates para‐ and meta‐halogenated, mildly electron‐rich and electron‐poor aromatic rings with excellent enantioselectivities and yields. The yield of the rearrangement diminished with highly electron‐rich aryl rings whereas very electron‐deficient and ortho‐substituted arenes led to poor enantiocontrol. A Hammett analysis demonstrated the migratory preference for electron‐rich aromatic rings, which is consistent with the intermediacy of a phenonium cation.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement ; day:06 ; month:11 ; year:2024 ; extent:8
Angewandte Chemie / International edition. International edition ; (06.11.2024) (gesamt 8)

Creator: Kalomenopoulos, Panagiotis G.
Emayavaramban, Balakumar
Johnston, Craig P.

DOI: 10.1002/anie.202414342

URN: urn:nbn:de:101:1-2411061403271.902560494603

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:37 AM CEST

Data provider

This object is provided by:
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.

Show original at data provider

Associated

Kalomenopoulos, Panagiotis G.
Emayavaramban, Balakumar
Johnston, Craig P.

Other Objects (12)

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

The Enantioselective Overman Rearrangement

The Enantioselective Overman Rearrangement

Enantioselective α-Functionalization of Ketones

Enantioselective α-Functionalization of Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

The Enantioselective Overman Rearrangement

The Enantioselective Overman Rearrangement

Enantioselective α-Functionalization of Ketones

Enantioselective α-Functionalization of Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Enantioselective Synthesis of α‐Aryl Ketones by a Cobalt‐Catalyzed Semipinacol Rearrangement

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Photoinduced Cobalt-Catalyzed Enantioselective Reductive Addition of Aryl Iodides to Aldehydes

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Enantioselective Cobalt-Catalyzed Alkene Hydroalkylation

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-catalyzed difluoroalkylation of tertiary aryl ketones for facile synthesis of quaternary alkyl difluorides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Cobalt-Catalyzed Enantioselective Hydrogenation of Enamides

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

Regio- and Enantioselective Cobalt-Catalyzed Allylic Amination

The Enantioselective Overman Rearrangement

The Enantioselective Overman Rearrangement

Enantioselective α-Functionalization of Ketones

Enantioselective α-Functionalization of Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Traceless Rhodium‐Catalyzed Hydroacylation Using Alkyl Aldehydes: The Enantioselective Synthesis of β‐Aryl Ketones

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

Cultural heritage institutions wishing to register will find more information here.

Fields marked * need to be filled in.

Username*

Please enter your username

Email*

Please enter your email address

Please do not fill this field

First name

Last name

Password*

Please enter your password

Confirm password*

Please enter the same password

I have read the terms of use and the privacy policy for the collection of personal data and accept them. *

This field is required.

I would like to subscribe to the newsletter of the Deutsche Digitale Bibliothek. See newsletter subscription info.

Account created

Your "My DDB" account has been successfully created. Before you can log in to your account, you must click the confirmation link in the message we just sent to the email address you provided.