Phosphite-mediated conversion of benzaldehydes into stilbenes via umpolung through a dioxaphospholane intermediate

Johannes Fabritius Petersen; Christian Tortzen; Frederik Præstholm Jørgensen; Christian Richard Parker; Mogens Brøndsted Nielsen

doi:10.1016/j.tetlet.2015.02.108

Phosphite-mediated conversion of benzaldehydes into stilbenes via umpolung through a dioxaphospholane intermediate

Johannes Fabritius Petersen, Christian Tortzen, Frederik Præstholm Jørgensen, Christian Richard Parker, Mogens Brøndsted Nielsen

8 Citations (Scopus)

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Abstract

The phosphite-mediated coupling of two benzaldehydes into 2,2,2-triethoxy-1,3,2-dioxaphospholanes was investigated using ¹³C NMR spectroscopy and was found to be very sensitive to the nature of the ortho/para substituents, and promoted by electron-withdrawing groups (EWGs). Stilbene-extended tetrathiafulvalenes were prepared by heating the intermediate dioxaphospholane, containing aldehyde substituents at para positions and ethynyl groups at ortho/meta positions, with 1,3-dithiol-2-thiones in P(OEt)₃. While EWGs promoted dioxaphospholane formation, electron-donating groups (EDGs), generated by conversion of the aldehydes into dithiafulvenes, promoted subsequent conversion into an alkene.

Original language	English
Journal	Tetrahedron Letters
Volume	56
Issue number	14
Pages (from-to)	1894-1897
Number of pages	4
ISSN	0040-4039
DOIs	https://doi.org/10.1016/j.tetlet.2015.02.108
Publication status	Published - 1 Apr 2015

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title = "Phosphite-mediated conversion of benzaldehydes into stilbenes via umpolung through a dioxaphospholane intermediate",

abstract = "The phosphite-mediated coupling of two benzaldehydes into 2,2,2-triethoxy-1,3,2-dioxaphospholanes was investigated using 13C NMR spectroscopy and was found to be very sensitive to the nature of the ortho/para substituents, and promoted by electron-withdrawing groups (EWGs). Stilbene-extended tetrathiafulvalenes were prepared by heating the intermediate dioxaphospholane, containing aldehyde substituents at para positions and ethynyl groups at ortho/meta positions, with 1,3-dithiol-2-thiones in P(OEt)3. While EWGs promoted dioxaphospholane formation, electron-donating groups (EDGs), generated by conversion of the aldehydes into dithiafulvenes, promoted subsequent conversion into an alkene.",

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doi = "10.1016/j.tetlet.2015.02.108",

language = "English",

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T1 - Phosphite-mediated conversion of benzaldehydes into stilbenes via umpolung through a dioxaphospholane intermediate

AU - Petersen, Johannes Fabritius

AU - Tortzen, Christian

AU - Jørgensen, Frederik Præstholm

AU - Parker, Christian Richard

AU - Nielsen, Mogens Brøndsted

PY - 2015/4/1

Y1 - 2015/4/1

N2 - The phosphite-mediated coupling of two benzaldehydes into 2,2,2-triethoxy-1,3,2-dioxaphospholanes was investigated using 13C NMR spectroscopy and was found to be very sensitive to the nature of the ortho/para substituents, and promoted by electron-withdrawing groups (EWGs). Stilbene-extended tetrathiafulvalenes were prepared by heating the intermediate dioxaphospholane, containing aldehyde substituents at para positions and ethynyl groups at ortho/meta positions, with 1,3-dithiol-2-thiones in P(OEt)3. While EWGs promoted dioxaphospholane formation, electron-donating groups (EDGs), generated by conversion of the aldehydes into dithiafulvenes, promoted subsequent conversion into an alkene.

AB - The phosphite-mediated coupling of two benzaldehydes into 2,2,2-triethoxy-1,3,2-dioxaphospholanes was investigated using 13C NMR spectroscopy and was found to be very sensitive to the nature of the ortho/para substituents, and promoted by electron-withdrawing groups (EWGs). Stilbene-extended tetrathiafulvalenes were prepared by heating the intermediate dioxaphospholane, containing aldehyde substituents at para positions and ethynyl groups at ortho/meta positions, with 1,3-dithiol-2-thiones in P(OEt)3. While EWGs promoted dioxaphospholane formation, electron-donating groups (EDGs), generated by conversion of the aldehydes into dithiafulvenes, promoted subsequent conversion into an alkene.

U2 - 10.1016/j.tetlet.2015.02.108

DO - 10.1016/j.tetlet.2015.02.108

M3 - Journal article

SN - 0040-4039

VL - 56

SP - 1894

EP - 1897

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 14

ER -

Phosphite-mediated conversion of benzaldehydes into stilbenes via umpolung through a dioxaphospholane intermediate

Abstract

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