Modification of Estradiol at the 17-Position. Effect of Changing the OH Group for a Transition-Metal Carbonyl Cluster on the Estradiol Receptor Recognition

Domenico Osella; Giorgia Dutto; Gérard Jaouen; Anne Vessiéres; Paul R. Raithby; Laura De Benedetto; Michael J. McGlinchey

doi:10.1021/om00035a045

Modification of Estradiol at the 17-Position. Effect of Changing the OH Group for a Transition-Metal Carbonyl Cluster on the Estradiol Receptor Recognition

Domenico Osella, Giorgia Dutto, Gérard Jaouen, Anne Vessiéres, Paul R. Raithby, Laura De Benedetto, Michael J. McGlinchey

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

Abstract

The reaction of [Co₂(CO)₆(17α-ethynyl-17β-estradiol)] (2a) with Fe(CO)₅ in acetone produces [FeCo(CO)₆(17α-ethynyl-17β-dehydroxyestradiol)] (3a) as the result of the dehydroxylation ability of the iron pentacarbonyl. The molecular structure of 3a has been investigated not only by NMR spectroscopy but also by use of molecular modeling techniques. The structural data for the organometallic part of the molecule are derived from a single-crystal X-ray determination of the model complex [FeCo(CO)₅(PPh₃)(H₃CC₂CH₂)], carried out at 123 K: triclinic, P1 (No. 2), a = 10.315(1) Å, b = 10.579(1) Å, c = 12.989(2) Å, α = 67.62(1)°, β = 89.44(2)°, γ = 79.30(2)°, V = 1287.1(7) Å³, Z = 2, R_F = 0.063. The mixed-metal cluster [FeCo(CO)₆(HCCCH₂)] was used as a model of the cation [Co₂(CO)₆(HCCCH₂)]⁺, and its structure was rationalized by means of extended Hückel molecular orbital calculations. The biological results obtained from the incubation in vitro of the steroid–organometallic complex 3a with lamb uterine cytosol (used as a source of estradiol receptor) indicate that the absence of the 17-OH group on estradiol prevents the formation of an irreversible (covalent) bond between the metal-labeled steroid and its specific receptor. The biochemical implications of such a change in reactivity are discussed.

Original language	English
Pages (from-to)	4545-4552
Number of pages	8
Journal	Organometallics
Volume	12
Issue number	11
DOIs	https://doi.org/10.1021/om00035a045
Publication status	Published - 1993
Externally published	Yes

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@article{c3a1e8df52a2492b82876727f2e1dbee,

title = "Modification of Estradiol at the 17-Position. Effect of Changing the OH Group for a Transition-Metal Carbonyl Cluster on the Estradiol Receptor Recognition",

abstract = "The reaction of [Co2(CO)6(17α-ethynyl-17β-estradiol)] (2a) with Fe(CO)5 in acetone produces [FeCo(CO)6(17α-ethynyl-17β-dehydroxyestradiol)] (3a) as the result of the dehydroxylation ability of the iron pentacarbonyl. The molecular structure of 3a has been investigated not only by NMR spectroscopy but also by use of molecular modeling techniques. The structural data for the organometallic part of the molecule are derived from a single-crystal X-ray determination of the model complex [FeCo(CO)5(PPh3)(H3CC2CH2)], carried out at 123 K: triclinic, P1 (No. 2), a = 10.315(1) {\AA}, b = 10.579(1) {\AA}, c = 12.989(2) {\AA}, α = 67.62(1)°, β = 89.44(2)°, γ = 79.30(2)°, V = 1287.1(7) {\AA}3, Z = 2, RF = 0.063. The mixed-metal cluster [FeCo(CO)6(HCCCH2)] was used as a model of the cation [Co2(CO)6(HCCCH2)]+, and its structure was rationalized by means of extended H{\"u}ckel molecular orbital calculations. The biological results obtained from the incubation in vitro of the steroid–organometallic complex 3a with lamb uterine cytosol (used as a source of estradiol receptor) indicate that the absence of the 17-OH group on estradiol prevents the formation of an irreversible (covalent) bond between the metal-labeled steroid and its specific receptor. The biochemical implications of such a change in reactivity are discussed.",

author = "Domenico Osella and Giorgia Dutto and G{\'e}rard Jaouen and Anne Vessi{\'e}res and Raithby, {Paul R.} and {De Benedetto}, Laura and McGlinchey, {Michael J.}",

year = "1993",

doi = "10.1021/om00035a045",

language = "English",

volume = "12",

pages = "4545--4552",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Modification of Estradiol at the 17-Position. Effect of Changing the OH Group for a Transition-Metal Carbonyl Cluster on the Estradiol Receptor Recognition

AU - Osella, Domenico

AU - Dutto, Giorgia

AU - Jaouen, Gérard

AU - Vessiéres, Anne

AU - Raithby, Paul R.

AU - De Benedetto, Laura

AU - McGlinchey, Michael J.

PY - 1993

Y1 - 1993

N2 - The reaction of [Co2(CO)6(17α-ethynyl-17β-estradiol)] (2a) with Fe(CO)5 in acetone produces [FeCo(CO)6(17α-ethynyl-17β-dehydroxyestradiol)] (3a) as the result of the dehydroxylation ability of the iron pentacarbonyl. The molecular structure of 3a has been investigated not only by NMR spectroscopy but also by use of molecular modeling techniques. The structural data for the organometallic part of the molecule are derived from a single-crystal X-ray determination of the model complex [FeCo(CO)5(PPh3)(H3CC2CH2)], carried out at 123 K: triclinic, P1 (No. 2), a = 10.315(1) Å, b = 10.579(1) Å, c = 12.989(2) Å, α = 67.62(1)°, β = 89.44(2)°, γ = 79.30(2)°, V = 1287.1(7) Å3, Z = 2, RF = 0.063. The mixed-metal cluster [FeCo(CO)6(HCCCH2)] was used as a model of the cation [Co2(CO)6(HCCCH2)]+, and its structure was rationalized by means of extended Hückel molecular orbital calculations. The biological results obtained from the incubation in vitro of the steroid–organometallic complex 3a with lamb uterine cytosol (used as a source of estradiol receptor) indicate that the absence of the 17-OH group on estradiol prevents the formation of an irreversible (covalent) bond between the metal-labeled steroid and its specific receptor. The biochemical implications of such a change in reactivity are discussed.

AB - The reaction of [Co2(CO)6(17α-ethynyl-17β-estradiol)] (2a) with Fe(CO)5 in acetone produces [FeCo(CO)6(17α-ethynyl-17β-dehydroxyestradiol)] (3a) as the result of the dehydroxylation ability of the iron pentacarbonyl. The molecular structure of 3a has been investigated not only by NMR spectroscopy but also by use of molecular modeling techniques. The structural data for the organometallic part of the molecule are derived from a single-crystal X-ray determination of the model complex [FeCo(CO)5(PPh3)(H3CC2CH2)], carried out at 123 K: triclinic, P1 (No. 2), a = 10.315(1) Å, b = 10.579(1) Å, c = 12.989(2) Å, α = 67.62(1)°, β = 89.44(2)°, γ = 79.30(2)°, V = 1287.1(7) Å3, Z = 2, RF = 0.063. The mixed-metal cluster [FeCo(CO)6(HCCCH2)] was used as a model of the cation [Co2(CO)6(HCCCH2)]+, and its structure was rationalized by means of extended Hückel molecular orbital calculations. The biological results obtained from the incubation in vitro of the steroid–organometallic complex 3a with lamb uterine cytosol (used as a source of estradiol receptor) indicate that the absence of the 17-OH group on estradiol prevents the formation of an irreversible (covalent) bond between the metal-labeled steroid and its specific receptor. The biochemical implications of such a change in reactivity are discussed.

UR - http://www.scopus.com/inward/record.url?scp=0001254467&partnerID=8YFLogxK

U2 - 10.1021/om00035a045

DO - 10.1021/om00035a045

M3 - Article

SN - 0276-7333

VL - 12

SP - 4545

EP - 4552

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Modification of Estradiol at the 17-Position. Effect of Changing the OH Group for a Transition-Metal Carbonyl Cluster on the Estradiol Receptor Recognition

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