Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes

Luis Azofra Mesa; Albert Poater

doi:10.1039/c9dt03379c

Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes

Luis Azofra Mesa, Albert Poater

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

19 Scopus citations

Abstract

The proposed reaction mechanism for the unprecedented direct transformation of primary alcohols into alkenes catalysed by Mn(I)-PNP complexes consists of two cycles. First, the acceptorless dehydrogenation of the alcohol into aldehyde is produced via a concerted mechanism. Secondly, in an excess of hydrazine, hydrazone is formed and reacts with the aldehyde to produce olefins. This process, taking place in base-free conditions, is characterised by the diastereoselective formation of diazenyl intermediates. Based on DFT data, the generation of the (SN,S,S) diastereoisomer is favoured over the rest, leading in its decomposition to the preferential formation of an (E)-alkene and liberating N2 and H2O as the only by-products.

Original language	English (US)
Pages (from-to)	14122-14127
Number of pages	6
Journal	Dalton Transactions
Volume	48
Issue number	37
DOIs	https://doi.org/10.1039/c9dt03379c
State	Published - Sep 4 2019
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes",

abstract = "The proposed reaction mechanism for the unprecedented direct transformation of primary alcohols into alkenes catalysed by Mn(I)-PNP complexes consists of two cycles. First, the acceptorless dehydrogenation of the alcohol into aldehyde is produced via a concerted mechanism. Secondly, in an excess of hydrazine, hydrazone is formed and reacts with the aldehyde to produce olefins. This process, taking place in base-free conditions, is characterised by the diastereoselective formation of diazenyl intermediates. Based on DFT data, the generation of the (SN,S,S) diastereoisomer is favoured over the rest, leading in its decomposition to the preferential formation of an (E)-alkene and liberating N2 and H2O as the only by-products.",

author = "{Azofra Mesa}, Luis and Albert Poater",

note = "KAUST Repository Item: Exported on 2022-06-07 Acknowledgements: L. M. A. is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). A. P. is a Serra H{\'u}nter Fellow, and thanks the Ministerio de Ciencia, Innovaci{\'o}n y Universidades (MICINN) for project PGC2018-097722-B-I00. We also acknowledge the KAUST Supercomputing Laboratory, using the supercomputer Shaheen II, for providing the computational resources. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2019",

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doi = "10.1039/c9dt03379c",

language = "English (US)",

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AU - Azofra Mesa, Luis

AU - Poater, Albert

N1 - KAUST Repository Item: Exported on 2022-06-07 Acknowledgements: L. M. A. is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). A. P. is a Serra Húnter Fellow, and thanks the Ministerio de Ciencia, Innovación y Universidades (MICINN) for project PGC2018-097722-B-I00. We also acknowledge the KAUST Supercomputing Laboratory, using the supercomputer Shaheen II, for providing the computational resources. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2019/9/4

Y1 - 2019/9/4

N2 - The proposed reaction mechanism for the unprecedented direct transformation of primary alcohols into alkenes catalysed by Mn(I)-PNP complexes consists of two cycles. First, the acceptorless dehydrogenation of the alcohol into aldehyde is produced via a concerted mechanism. Secondly, in an excess of hydrazine, hydrazone is formed and reacts with the aldehyde to produce olefins. This process, taking place in base-free conditions, is characterised by the diastereoselective formation of diazenyl intermediates. Based on DFT data, the generation of the (SN,S,S) diastereoisomer is favoured over the rest, leading in its decomposition to the preferential formation of an (E)-alkene and liberating N2 and H2O as the only by-products.

AB - The proposed reaction mechanism for the unprecedented direct transformation of primary alcohols into alkenes catalysed by Mn(I)-PNP complexes consists of two cycles. First, the acceptorless dehydrogenation of the alcohol into aldehyde is produced via a concerted mechanism. Secondly, in an excess of hydrazine, hydrazone is formed and reacts with the aldehyde to produce olefins. This process, taking place in base-free conditions, is characterised by the diastereoselective formation of diazenyl intermediates. Based on DFT data, the generation of the (SN,S,S) diastereoisomer is favoured over the rest, leading in its decomposition to the preferential formation of an (E)-alkene and liberating N2 and H2O as the only by-products.

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DO - 10.1039/c9dt03379c

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SN - 1477-9234

VL - 48

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EP - 14127

JO - Dalton Transactions

JF - Dalton Transactions

IS - 37

ER -

Diastereoselective diazenyl formation: the key for manganese-catalysed alcohol conversion into (E)-alkenes

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