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Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes
Vicinal amino alcohols of steroids have been used as starting materials for the synthesis of chiral ligands with defined arrangements of functional groups. Condensation of the four diastereomeric 16,17-steroid amino alcohols 1a– 1d with aromatic o-hydroxy and heteroaromatic α-aldehydes afforded the...
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| Published in: | Steroids 2000-06, Vol.65 (6), p.305-318 |
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| creator | Dubs, Manuela Krieg, Reimar Görls, Helmar Schönecker, Bruno |
| description | Vicinal amino alcohols of steroids have been used as starting materials for the synthesis of chiral ligands with defined arrangements of functional groups. Condensation of the four diastereomeric 16,17-steroid amino alcohols
1a–
1d with aromatic o-hydroxy and heteroaromatic α-aldehydes afforded the
Schiff bases
2–6. When the 16,17-substituted compounds
2d,
5d,
6a, and
6d were in solution, the isomeric oxazolidines were detectable by
1H NMR spectroscopy. The formation of oxazolidines could be avoided by using bulky aldehydes. Reduction of the
Schiff bases (also in mixtures with oxazolidines) with NaBH
4 yielded the new
N-substituted amino alcohols
12–15. The condensation products of
1a–
1d with 1,3-dicarbonyl compounds (
7 and
8) exhibited the 1-enamino-3-oxo structure (
1H NMR spectroscopy). By means of X-ray analysis of
2a–
2d,
3d,
7a, and
7c, the torsion angles for the 16N, 17O substituents, which are important for a participation of the 17O substituent in the complexation of metal ions, have been determined. Furthermore, a preferred arrangement between the chelate ring and the steroid plane existed in all investigated condensation products attributable to torsion angles 16H-C16–16N-C of 5–61°. This arrangement was also preserved in the copper(II) complex
11 with 16α,17β-
trans configuration of the bidentate steroid ligand and a ratio of 2:1 for ligand: copper in contrast with dimeric copper(II) complexes with a tridentate steroid ligand of 16β,17β-
cis configuration (ratio of 1:1 for ligand:copper). The crystal structures of the condensation products are also discussed. In most cases, intermolecular hydrogen bonds between 17-hydroxy groups and the chelate oxygen caused polymeric strands. |
| doi_str_mv | 10.1016/S0039-128X(00)00092-1 |
| format | article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_71099543</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><els_id>S0039128X00000921</els_id><sourcerecordid>71099543</sourcerecordid><originalsourceid>FETCH-LOGICAL-c305t-827e976a31acdc619e1a4cda96027ddf75f4c57e283480a5435a7fe324e102603</originalsourceid><addsrcrecordid>eNqFkUtuFDEQhhsURIbAEUBeoGhGiqHc716hKOIxUiQkHhI7q2JXa4y62xPbDZkdh-AiXIRDcBLcPUNgx8qW6vv_evxJ8ljAMwGifP4eIGu4SOtPS4AVADQpF3eThairmhd1WR0li1vkOHng_ecIlVmT3k-OBdSQprVY3Dl6R6iCsYNntmVhQ6y1o2PaoA_kyPbkjGKi5NibwXJR8c1OO3uz4xnvKWymH_ngkIuz7KxYCljx4AwN5NlXEzYMne0xRA_rIv1HzXDQbEOxhb0Ffv7g2GmKRNRO9Vkfbbk2Ct2VHXYdU7bf2nHQ_te3773tSI0dOhYHGFUYHc1bKDtoGjxOa7GtszrW9o5zcbslt1yvV7NXRzfkHyb3Wuw8PTq8J8nHVy8_XLzhl29fry_OL7nKoAi8TitqqhIzgUqrUjQkMFcamxLSSuu2KtpcFRWldZbXgEWeFVi1lKU5CUhLyE6S071vHOp6jGeTvfGKug4HsqOXlYCmibIIFntQOeu9o1ZunenR7aQAOcUv5_jllK0EkHP8UkTdk0OD8aon_Y9qn3cEnh4A9Aq71uGgjP_L5dDEGSL2Yo9RvMYXQ056FTNVpI0jFaS25j-T_AaZOdJO</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>71099543</pqid></control><display><type>article</type><title>Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes</title><source>ScienceDirect Freedom Collection</source><creator>Dubs, Manuela ; Krieg, Reimar ; Görls, Helmar ; Schönecker, Bruno</creator><creatorcontrib>Dubs, Manuela ; Krieg, Reimar ; Görls, Helmar ; Schönecker, Bruno</creatorcontrib><description>Vicinal amino alcohols of steroids have been used as starting materials for the synthesis of chiral ligands with defined arrangements of functional groups. Condensation of the four diastereomeric 16,17-steroid amino alcohols
1a–
1d with aromatic o-hydroxy and heteroaromatic α-aldehydes afforded the
Schiff bases
2–6. When the 16,17-substituted compounds
2d,
5d,
6a, and
6d were in solution, the isomeric oxazolidines were detectable by
1H NMR spectroscopy. The formation of oxazolidines could be avoided by using bulky aldehydes. Reduction of the
Schiff bases (also in mixtures with oxazolidines) with NaBH
4 yielded the new
N-substituted amino alcohols
12–15. The condensation products of
1a–
1d with 1,3-dicarbonyl compounds (
7 and
8) exhibited the 1-enamino-3-oxo structure (
1H NMR spectroscopy). By means of X-ray analysis of
2a–
2d,
3d,
7a, and
7c, the torsion angles for the 16N, 17O substituents, which are important for a participation of the 17O substituent in the complexation of metal ions, have been determined. Furthermore, a preferred arrangement between the chelate ring and the steroid plane existed in all investigated condensation products attributable to torsion angles 16H-C16–16N-C of 5–61°. This arrangement was also preserved in the copper(II) complex
11 with 16α,17β-
trans configuration of the bidentate steroid ligand and a ratio of 2:1 for ligand: copper in contrast with dimeric copper(II) complexes with a tridentate steroid ligand of 16β,17β-
cis configuration (ratio of 1:1 for ligand:copper). The crystal structures of the condensation products are also discussed. In most cases, intermolecular hydrogen bonds between 17-hydroxy groups and the chelate oxygen caused polymeric strands.</description><identifier>ISSN: 0039-128X</identifier><identifier>EISSN: 1878-5867</identifier><identifier>DOI: 10.1016/S0039-128X(00)00092-1</identifier><identifier>PMID: 10802281</identifier><identifier>CODEN: STEDAM</identifier><language>eng</language><publisher>New York, NY: Elsevier Inc</publisher><subject>Aldehydes - chemistry ; Alicyclic compounds, terpenoids, prostaglandins, steroids ; Amino alcohol derivatives ; Amino Alcohols - chemistry ; Chemistry ; Condensed matter: structure, mechanical and thermal properties ; Copper - chemistry ; Copper complexes ; Exact sciences and technology ; Hydrogen Bonding ; Inorganic compounds ; Ligands ; Magnetic Resonance Spectroscopy ; Metal complexes ; Molecular Structure ; Organic chemistry ; Physics ; Preparations and properties ; Schiff bases ; Steroids ; Structure of solids and liquids; crystallography ; Structure of specific crystalline solids ; X-ray analysis ; X-Ray Diffraction</subject><ispartof>Steroids, 2000-06, Vol.65 (6), p.305-318</ispartof><rights>2000 Elsevier Science Inc.</rights><rights>2000 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c305t-827e976a31acdc619e1a4cda96027ddf75f4c57e283480a5435a7fe324e102603</citedby><cites>FETCH-LOGICAL-c305t-827e976a31acdc619e1a4cda96027ddf75f4c57e283480a5435a7fe324e102603</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=1409109$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/10802281$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Dubs, Manuela</creatorcontrib><creatorcontrib>Krieg, Reimar</creatorcontrib><creatorcontrib>Görls, Helmar</creatorcontrib><creatorcontrib>Schönecker, Bruno</creatorcontrib><title>Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes</title><title>Steroids</title><addtitle>Steroids</addtitle><description>Vicinal amino alcohols of steroids have been used as starting materials for the synthesis of chiral ligands with defined arrangements of functional groups. Condensation of the four diastereomeric 16,17-steroid amino alcohols
1a–
1d with aromatic o-hydroxy and heteroaromatic α-aldehydes afforded the
Schiff bases
2–6. When the 16,17-substituted compounds
2d,
5d,
6a, and
6d were in solution, the isomeric oxazolidines were detectable by
1H NMR spectroscopy. The formation of oxazolidines could be avoided by using bulky aldehydes. Reduction of the
Schiff bases (also in mixtures with oxazolidines) with NaBH
4 yielded the new
N-substituted amino alcohols
12–15. The condensation products of
1a–
1d with 1,3-dicarbonyl compounds (
7 and
8) exhibited the 1-enamino-3-oxo structure (
1H NMR spectroscopy). By means of X-ray analysis of
2a–
2d,
3d,
7a, and
7c, the torsion angles for the 16N, 17O substituents, which are important for a participation of the 17O substituent in the complexation of metal ions, have been determined. Furthermore, a preferred arrangement between the chelate ring and the steroid plane existed in all investigated condensation products attributable to torsion angles 16H-C16–16N-C of 5–61°. This arrangement was also preserved in the copper(II) complex
11 with 16α,17β-
trans configuration of the bidentate steroid ligand and a ratio of 2:1 for ligand: copper in contrast with dimeric copper(II) complexes with a tridentate steroid ligand of 16β,17β-
cis configuration (ratio of 1:1 for ligand:copper). The crystal structures of the condensation products are also discussed. In most cases, intermolecular hydrogen bonds between 17-hydroxy groups and the chelate oxygen caused polymeric strands.</description><subject>Aldehydes - chemistry</subject><subject>Alicyclic compounds, terpenoids, prostaglandins, steroids</subject><subject>Amino alcohol derivatives</subject><subject>Amino Alcohols - chemistry</subject><subject>Chemistry</subject><subject>Condensed matter: structure, mechanical and thermal properties</subject><subject>Copper - chemistry</subject><subject>Copper complexes</subject><subject>Exact sciences and technology</subject><subject>Hydrogen Bonding</subject><subject>Inorganic compounds</subject><subject>Ligands</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Metal complexes</subject><subject>Molecular Structure</subject><subject>Organic chemistry</subject><subject>Physics</subject><subject>Preparations and properties</subject><subject>Schiff bases</subject><subject>Steroids</subject><subject>Structure of solids and liquids; crystallography</subject><subject>Structure of specific crystalline solids</subject><subject>X-ray analysis</subject><subject>X-Ray Diffraction</subject><issn>0039-128X</issn><issn>1878-5867</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><recordid>eNqFkUtuFDEQhhsURIbAEUBeoGhGiqHc716hKOIxUiQkHhI7q2JXa4y62xPbDZkdh-AiXIRDcBLcPUNgx8qW6vv_evxJ8ljAMwGifP4eIGu4SOtPS4AVADQpF3eThairmhd1WR0li1vkOHng_ecIlVmT3k-OBdSQprVY3Dl6R6iCsYNntmVhQ6y1o2PaoA_kyPbkjGKi5NibwXJR8c1OO3uz4xnvKWymH_ngkIuz7KxYCljx4AwN5NlXEzYMne0xRA_rIv1HzXDQbEOxhb0Ffv7g2GmKRNRO9Vkfbbk2Ct2VHXYdU7bf2nHQ_te3773tSI0dOhYHGFUYHc1bKDtoGjxOa7GtszrW9o5zcbslt1yvV7NXRzfkHyb3Wuw8PTq8J8nHVy8_XLzhl29fry_OL7nKoAi8TitqqhIzgUqrUjQkMFcamxLSSuu2KtpcFRWldZbXgEWeFVi1lKU5CUhLyE6S071vHOp6jGeTvfGKug4HsqOXlYCmibIIFntQOeu9o1ZunenR7aQAOcUv5_jllK0EkHP8UkTdk0OD8aon_Y9qn3cEnh4A9Aq71uGgjP_L5dDEGSL2Yo9RvMYXQ056FTNVpI0jFaS25j-T_AaZOdJO</recordid><startdate>200006</startdate><enddate>200006</enddate><creator>Dubs, Manuela</creator><creator>Krieg, Reimar</creator><creator>Görls, Helmar</creator><creator>Schönecker, Bruno</creator><general>Elsevier Inc</general><general>Elsevier Science</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>200006</creationdate><title>Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes</title><author>Dubs, Manuela ; Krieg, Reimar ; Görls, Helmar ; Schönecker, Bruno</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c305t-827e976a31acdc619e1a4cda96027ddf75f4c57e283480a5435a7fe324e102603</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><topic>Aldehydes - chemistry</topic><topic>Alicyclic compounds, terpenoids, prostaglandins, steroids</topic><topic>Amino alcohol derivatives</topic><topic>Amino Alcohols - chemistry</topic><topic>Chemistry</topic><topic>Condensed matter: structure, mechanical and thermal properties</topic><topic>Copper - chemistry</topic><topic>Copper complexes</topic><topic>Exact sciences and technology</topic><topic>Hydrogen Bonding</topic><topic>Inorganic compounds</topic><topic>Ligands</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Metal complexes</topic><topic>Molecular Structure</topic><topic>Organic chemistry</topic><topic>Physics</topic><topic>Preparations and properties</topic><topic>Schiff bases</topic><topic>Steroids</topic><topic>Structure of solids and liquids; crystallography</topic><topic>Structure of specific crystalline solids</topic><topic>X-ray analysis</topic><topic>X-Ray Diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dubs, Manuela</creatorcontrib><creatorcontrib>Krieg, Reimar</creatorcontrib><creatorcontrib>Görls, Helmar</creatorcontrib><creatorcontrib>Schönecker, Bruno</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Steroids</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Dubs, Manuela</au><au>Krieg, Reimar</au><au>Görls, Helmar</au><au>Schönecker, Bruno</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes</atitle><jtitle>Steroids</jtitle><addtitle>Steroids</addtitle><date>2000-06</date><risdate>2000</risdate><volume>65</volume><issue>6</issue><spage>305</spage><epage>318</epage><pages>305-318</pages><issn>0039-128X</issn><eissn>1878-5867</eissn><coden>STEDAM</coden><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><abstract>Vicinal amino alcohols of steroids have been used as starting materials for the synthesis of chiral ligands with defined arrangements of functional groups. Condensation of the four diastereomeric 16,17-steroid amino alcohols
1a–
1d with aromatic o-hydroxy and heteroaromatic α-aldehydes afforded the
Schiff bases
2–6. When the 16,17-substituted compounds
2d,
5d,
6a, and
6d were in solution, the isomeric oxazolidines were detectable by
1H NMR spectroscopy. The formation of oxazolidines could be avoided by using bulky aldehydes. Reduction of the
Schiff bases (also in mixtures with oxazolidines) with NaBH
4 yielded the new
N-substituted amino alcohols
12–15. The condensation products of
1a–
1d with 1,3-dicarbonyl compounds (
7 and
8) exhibited the 1-enamino-3-oxo structure (
1H NMR spectroscopy). By means of X-ray analysis of
2a–
2d,
3d,
7a, and
7c, the torsion angles for the 16N, 17O substituents, which are important for a participation of the 17O substituent in the complexation of metal ions, have been determined. Furthermore, a preferred arrangement between the chelate ring and the steroid plane existed in all investigated condensation products attributable to torsion angles 16H-C16–16N-C of 5–61°. This arrangement was also preserved in the copper(II) complex
11 with 16α,17β-
trans configuration of the bidentate steroid ligand and a ratio of 2:1 for ligand: copper in contrast with dimeric copper(II) complexes with a tridentate steroid ligand of 16β,17β-
cis configuration (ratio of 1:1 for ligand:copper). The crystal structures of the condensation products are also discussed. In most cases, intermolecular hydrogen bonds between 17-hydroxy groups and the chelate oxygen caused polymeric strands.</abstract><cop>New York, NY</cop><pub>Elsevier Inc</pub><pmid>10802281</pmid><doi>10.1016/S0039-128X(00)00092-1</doi><tpages>14</tpages></addata></record> |
| fulltext | fulltext |
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| ispartof | Steroids, 2000-06, Vol.65 (6), p.305-318 |
| issn | 0039-128X 1878-5867 |
| language | eng |
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| source | ScienceDirect Freedom Collection |
| subjects | Aldehydes - chemistry Alicyclic compounds, terpenoids, prostaglandins, steroids Amino alcohol derivatives Amino Alcohols - chemistry Chemistry Condensed matter: structure, mechanical and thermal properties Copper - chemistry Copper complexes Exact sciences and technology Hydrogen Bonding Inorganic compounds Ligands Magnetic Resonance Spectroscopy Metal complexes Molecular Structure Organic chemistry Physics Preparations and properties Schiff bases Steroids Structure of solids and liquids crystallography Structure of specific crystalline solids X-ray analysis X-Ray Diffraction |
| title | Reactions of the four diastereomeric 16-amino-17-hydroxy-3-methoxy-estra-1,3,5(10)-trienes with aromatic ortho-hydroxy and heteroaromatic α-aldehydes and with 1,3-dicarbonyl compounds—molecular structures of condensation products and of copper(II) complexes |
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