Inorganic asymmetric synthesis: Asymmetric synthesis of a two-bladed propeller, octahedral metal complex

Rebecca J. Warr; Anthony C. Willis; S. Bruce Wild

doi:10.1021/ic060856q

Inorganic asymmetric synthesis: Asymmetric synthesis of a two-bladed propeller, octahedral metal complex

Rebecca J. Warr
, Anthony C. Willis
, S. Bruce Wild^*

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

A C₂ hexadentate, in which two pyridine-2-aldehyde 2′-pyridylhydrazone (PAPHY) groups are linked to a chiral auxiliary derived from (R,R)-tartaric acid, (R,R)-1, reacts with iron(II) benzenesulfonate to give the two-bladed propeller, octahedral complex (P_Fe)-[Fe{(R,R) -1}](PhSO₃)₂ with complete diastereoselectivity, as determined by ¹H NMR spectroscopy and X-ray crystallography. Saponification of the ester linkages and deprotonation of the hydrazone-NH groups in the configurationally pure diastereomer affords the complex (P _Fe)-[Fe(5-HOCH₂PAPY)₂] with 85% retention of configuration at the iron stereocenter, as determined by reprotonation of the neutral complex with enantiomerically pure (aR)-binaphthyl phosphoric acid and analysis of the ¹H NMR spectrum of the mixture of diastereomeric salts produced. This is the first asymmetric synthesis of a two-bladed propeller, octahedral metal complex by the classical organic methodology of chiral auxiliary-directed, asymmetric synthesis.

Original language	English
Pages (from-to)	8618-8627
Number of pages	10
Journal	Inorganic Chemistry
Volume	45
Issue number	21
DOIs	https://doi.org/10.1021/ic060856q
Publication status	Published - 16 Oct 2006

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@article{bc55ea5b66e841a2818325bc90742240,

title = "Inorganic asymmetric synthesis: Asymmetric synthesis of a two-bladed propeller, octahedral metal complex",

abstract = "A C2 hexadentate, in which two pyridine-2-aldehyde 2′-pyridylhydrazone (PAPHY) groups are linked to a chiral auxiliary derived from (R,R)-tartaric acid, (R,R)-1, reacts with iron(II) benzenesulfonate to give the two-bladed propeller, octahedral complex (PFe)-[Fe\{(R,R) -1\}](PhSO3)2 with complete diastereoselectivity, as determined by 1H NMR spectroscopy and X-ray crystallography. Saponification of the ester linkages and deprotonation of the hydrazone-NH groups in the configurationally pure diastereomer affords the complex (P Fe)-[Fe(5-HOCH2PAPY)2] with 85\% retention of configuration at the iron stereocenter, as determined by reprotonation of the neutral complex with enantiomerically pure (aR)-binaphthyl phosphoric acid and analysis of the 1H NMR spectrum of the mixture of diastereomeric salts produced. This is the first asymmetric synthesis of a two-bladed propeller, octahedral metal complex by the classical organic methodology of chiral auxiliary-directed, asymmetric synthesis.",

author = "Warr, \{Rebecca J.\} and Willis, \{Anthony C.\} and Wild, \{S. Bruce\}",

year = "2006",

month = oct,

day = "16",

doi = "10.1021/ic060856q",

language = "English",

volume = "45",

pages = "8618--8627",

journal = "Inorganic Chemistry",

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T1 - Inorganic asymmetric synthesis

T2 - Asymmetric synthesis of a two-bladed propeller, octahedral metal complex

AU - Warr, Rebecca J.

AU - Willis, Anthony C.

AU - Wild, S. Bruce

PY - 2006/10/16

Y1 - 2006/10/16

N2 - A C2 hexadentate, in which two pyridine-2-aldehyde 2′-pyridylhydrazone (PAPHY) groups are linked to a chiral auxiliary derived from (R,R)-tartaric acid, (R,R)-1, reacts with iron(II) benzenesulfonate to give the two-bladed propeller, octahedral complex (PFe)-[Fe{(R,R) -1}](PhSO3)2 with complete diastereoselectivity, as determined by 1H NMR spectroscopy and X-ray crystallography. Saponification of the ester linkages and deprotonation of the hydrazone-NH groups in the configurationally pure diastereomer affords the complex (P Fe)-[Fe(5-HOCH2PAPY)2] with 85% retention of configuration at the iron stereocenter, as determined by reprotonation of the neutral complex with enantiomerically pure (aR)-binaphthyl phosphoric acid and analysis of the 1H NMR spectrum of the mixture of diastereomeric salts produced. This is the first asymmetric synthesis of a two-bladed propeller, octahedral metal complex by the classical organic methodology of chiral auxiliary-directed, asymmetric synthesis.

AB - A C2 hexadentate, in which two pyridine-2-aldehyde 2′-pyridylhydrazone (PAPHY) groups are linked to a chiral auxiliary derived from (R,R)-tartaric acid, (R,R)-1, reacts with iron(II) benzenesulfonate to give the two-bladed propeller, octahedral complex (PFe)-[Fe{(R,R) -1}](PhSO3)2 with complete diastereoselectivity, as determined by 1H NMR spectroscopy and X-ray crystallography. Saponification of the ester linkages and deprotonation of the hydrazone-NH groups in the configurationally pure diastereomer affords the complex (P Fe)-[Fe(5-HOCH2PAPY)2] with 85% retention of configuration at the iron stereocenter, as determined by reprotonation of the neutral complex with enantiomerically pure (aR)-binaphthyl phosphoric acid and analysis of the 1H NMR spectrum of the mixture of diastereomeric salts produced. This is the first asymmetric synthesis of a two-bladed propeller, octahedral metal complex by the classical organic methodology of chiral auxiliary-directed, asymmetric synthesis.

UR - https://www.scopus.com/pages/publications/33750356716

U2 - 10.1021/ic060856q

DO - 10.1021/ic060856q

M3 - Article

SN - 0020-1669

VL - 45

SP - 8618

EP - 8627

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Inorganic asymmetric synthesis: Asymmetric synthesis of a two-bladed propeller, octahedral metal complex

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