Remote nucleophilic allylation by allylrhodium chain walking

Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking...

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Main Authors: Groves, Alistair, Martinez, Jose I., Smith, Joshua J., Lam, Hon Wai
Format: Article
Published: Wiley 2018
Subjects:
Online Access:https://eprints.nottingham.ac.uk/53051/
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author Groves, Alistair
Martinez, Jose I.
Smith, Joshua J.
Lam, Hon Wai
author_facet Groves, Alistair
Martinez, Jose I.
Smith, Joshua J.
Lam, Hon Wai
author_sort Groves, Alistair
building Nottingham Research Data Repository
collection Online Access
description Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and an imine to give Z-homoallylic alcohols and amines, respectively.
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spelling nottingham-530512020-05-04T19:46:04Z https://eprints.nottingham.ac.uk/53051/ Remote nucleophilic allylation by allylrhodium chain walking Groves, Alistair Martinez, Jose I. Smith, Joshua J. Lam, Hon Wai Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and an imine to give Z-homoallylic alcohols and amines, respectively. Wiley 2018-07-13 Article PeerReviewed Groves, Alistair, Martinez, Jose I., Smith, Joshua J. and Lam, Hon Wai (2018) Remote nucleophilic allylation by allylrhodium chain walking. Chemistry - A European Journal . ISSN 0947-6539 allylation chain walking homogenous catalysis isomerization rhodium https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201803574 doi:10.1002/chem.201803574 doi:10.1002/chem.201803574
spellingShingle allylation
chain walking
homogenous catalysis
isomerization
rhodium
Groves, Alistair
Martinez, Jose I.
Smith, Joshua J.
Lam, Hon Wai
Remote nucleophilic allylation by allylrhodium chain walking
title Remote nucleophilic allylation by allylrhodium chain walking
title_full Remote nucleophilic allylation by allylrhodium chain walking
title_fullStr Remote nucleophilic allylation by allylrhodium chain walking
title_full_unstemmed Remote nucleophilic allylation by allylrhodium chain walking
title_short Remote nucleophilic allylation by allylrhodium chain walking
title_sort remote nucleophilic allylation by allylrhodium chain walking
topic allylation
chain walking
homogenous catalysis
isomerization
rhodium
url https://eprints.nottingham.ac.uk/53051/
https://eprints.nottingham.ac.uk/53051/
https://eprints.nottingham.ac.uk/53051/