1,1′-Bi-2-naphthol: Difference between revisions
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{{chembox |
{{chembox |
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| verifiedrevid = 413087241 |
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| Name = 1,1{{prime}}-Bi-2-naphthol |
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| ImageFile = |
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| ImageSizeL1 = 100px |
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| ImageFileL1 = R-BINOL-2D-skeletal.png |
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| ImageNameL1 = Skeletal formula of R-BINOL |
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| ImageSizeR1 = 100px |
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| ImageNameR1 = Skeletal formula of S-BINOL |
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| ImageFileL2 = R-BINOL-3D-balls.png |
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| ImageNameL2 = Ball-and-stick model of R-BINOL |
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| ImageSize2 = 150px |
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| ImageNameR2 = Ball-and-stick model of S-BINOL |
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| OtherNames = 1,1'-Bi-2,2'-naphthol<br />1,1-Binaphthol<br />BINOL |
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| ImageCaptionL2 = (''R'')-(+)-BINOL |
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| ImageCaptionR2 = (''S'')-(−)-BINOL |
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| OtherNames = {{Unbulleted list |
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| 1,1-Binaphthol |
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| BINOL |
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| Binol |
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| SystematicName = |
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| Section1 = {{Chembox Identifiers |
| Section1 = {{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 11269 |
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| PubChem = 11762 |
| PubChem = 11762 |
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| InChI = 1/C20H14O2/c21-17-11-9-13-5-1-3-7-15(13)19(17)20-16-8-4-2-6-14(16)10-12-18(20)22/h1-12,21-22H |
| InChI = 1/C20H14O2/c21-17-11-9-13-5-1-3-7-15(13)19(17)20-16-8-4-2-6-14(16)10-12-18(20)22/h1-12,21-22H |
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| InChIKey = PPTXVXKCQZKFBN-UHFFFAOYAX |
| InChIKey = PPTXVXKCQZKFBN-UHFFFAOYAX |
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| SMILES = C1=CC=C2C(=C1)C=CC(=C2C3=C(C=CC4=CC=CC=C43)O)O |
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| SMILES1 = c1ccc2c(c1)ccc(c2c3c4ccccc4ccc3O)O |
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| SMILES_Comment = (''R''/''S'') |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 138718 |
| ChEMBL = 138718 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C20H14O2/c21-17-11-9-13-5-1-3-7-15(13)19(17)20-16-8-4-2-6-14(16)10-12-18(20)22/h1-12,21-22H |
| StdInChI = 1S/C20H14O2/c21-17-11-9-13-5-1-3-7-15(13)19(17)20-16-8-4-2-6-14(16)10-12-18(20)22/h1-12,21-22H |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = PPTXVXKCQZKFBN-UHFFFAOYSA-N |
| StdInChIKey = PPTXVXKCQZKFBN-UHFFFAOYSA-N |
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| CASNo = 602-09-5 |
| CASNo = 602-09-5 |
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| CASNo_Comment = (R/S) |
| CASNo_Comment = (''R''/''S'') |
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| CASNo1 = 18531-94-7 |
| CASNo1 = 18531-94-7 |
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| CASNo1_Comment = ( |
| CASNo1_Comment = (''R'')-(+) |
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| CASNo2 = 18531-99-2 |
| CASNo2 = 18531-99-2 |
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| CASNo2_Comment = (S)-( |
| CASNo2_Comment = (''S'')-(−) |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| SMILES = Oc4ccc1c(cccc1)c4c2c3c(ccc2O)cccc3 |
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| UNII = 25AB254328 |
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| UNII_Comment = (''R''/''S'') |
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| UNII1_Ref = {{fdacite|correct|FDA}} |
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| UNII1 = M6IDZ128WT |
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| UNII1_Comment = (''R'')-(+) |
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| UNII2_Ref = {{fdacite|correct|FDA}} |
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| UNII2 = 54OT5RRV4C |
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| UNII2_Comment = (''S'')-(−) |
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}} |
}} |
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| Section2 = {{Chembox Properties |
| Section2 = {{Chembox Properties |
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| Formula = |
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| Formula = C<sub>20</sub>H<sub>14</sub>O<sub>2</sub> |
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| C=20 | H=14 | O=2 |
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| MolarMass = 286.32 g/mol |
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| Density = |
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| MeltingPtC = 205 to 211 |
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}} |
}} |
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| Section3 = |
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| Section4 = |
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| Section5 = |
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| Section6 = |
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}} |
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'''1,1 |
'''1,1{{prime}}-Bi-2-naphthol''' ('''BINOL''') is an [[organic compound]] that is often used as a [[ligand]] for transition-metal catalysed [[asymmetric synthesis]]. BINOL has [[axial chirality]] and the two [[enantiomer]]s can be readily separated and are stable toward [[racemisation]]. The [[specific rotation]] of the two [[enantiomers]] is 35.5° (''c'' = 1 in [[THF]]), with the ''R'' enantiomer being the [[dextrorotary]] one. BINOL is a precursor for another [[chiral ligand]] called [[BINAP]]. The volumetric mass [[density]] of the two enantiomers is 0.62 g cm{{sup|−3}}.{{citation needed|date=January 2022}} |
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==Preparation== |
==Preparation== |
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The [[organic synthesis]] of BINOL is not a challenge as such but the preparation of the individual [[enantiomer]]s is. |
The [[organic synthesis]] of BINOL is not a challenge as such but the preparation of the individual [[enantiomer]]s is. |
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(''S'')-BINOL can be prepared directly from an asymmetric [[oxidative coupling]] of [[2-naphthol]] with [[copper(II) chloride]]. The [[chiral ligand]] in this reaction is (''S'')-(+)-[[amphetamine]].<ref> |
(''S'')-BINOL can be prepared directly from an asymmetric [[oxidative coupling]] of [[2-naphthol]] with [[copper(II) chloride]]. The [[chiral ligand]] in this reaction is (''S'')-(+)-[[amphetamine]].<ref>{{cite journal|last1 = Brussee|first1 = J.|last2 = Jansen|first2 = A. C. A.|year = 1983|title = A highly stereoselective synthesis of ''S''-(−)-[1,1{{prime}}-binaphthalene]-2,2{{prime}}-diol|journal = Tetrahedron Letters|volume = 24|issue = 31|pages = 3261–3262|doi = 10.1016/S0040-4039(00)88151-4}}</ref> |
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{{cite journal |
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| last = Brussee |
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| first = J. |
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| coauthors = Jansen A. C. A. |
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| year = 1983 |
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| title = A highly stereoselective synthesis of s(-)-[1,1′-binaphthalene]-2,2′-diol |
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| journal = Tetrahedron Letters |
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| volume = 24 |
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| pages = 3261–3262 |
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| doi = 10.1016/S0040-4039(00)88151-4 |
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</ref> |
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[[ |
[[File:CuCl2 naphthol coupling.png|400px]] |
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Racemic BINOL can also be produced using [[iron(III) chloride]] as an oxidant. The mechanism involves complexation of iron(III) into the [[hydroxyl]], followed by a radical coupling reaction of the naphthol rings initiated by iron(III) reducing into iron(II). |
Racemic BINOL can also be produced using [[iron(III) chloride]] as an oxidant. The mechanism involves complexation of iron(III) into the [[hydroxyl]], followed by a radical coupling reaction of the naphthol rings initiated by iron(III) reducing into iron(II). |
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[[Optically active]] BINOL can also be obtained from [[racemic]] BINOL by optical resolution. In one method, the [[alkaloid]] N-benzylcinchonidinium chloride |
[[Optically active]] BINOL can also be obtained from [[racemic]] BINOL by optical resolution. In one method, the [[alkaloid]] N-benzylcinchonidinium chloride forms a crystalline [[inclusion compound]]. The inclusion compound of the (''S'')-enantiomer is soluble in [[acetonitrile]] but that of the (''R'')-enantiomer is not.<ref name="orgsyn">[http://www.orgsyn.org/orgsyn/prep.asp?prep=v76p0001 "RESOLUTION OF 1,1'-BI-2-NAPHTHOL"] {{Webarchive|url=https://web.archive.org/web/20120716191712/http://www.orgsyn.org/orgsyn/prep.asp?prep=v76p0001 |date=2012-07-16 }}, Dongwei Cai, David L. Hughes, Thomas R. Verhoeven, and Paul J. Reider, in [[Organic Syntheses]] Coll. Vol. 10, p.93; Vol. 76, p.1</ref> In another method BINOL is esterified with [[pentanoyl chloride]]. The enzyme [[cholesterol]] [[esterase]] [[Hydrolysis|hydrolyse]]s the (''S'')-diester but not the (''R'')-diester.<ref name="orgsyn" /> The (''R'')-dipentanoate is hydrolysed in a second step with [[sodium methoxide]].<ref name="orgsyn2">[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv9p0077 "(''S'')-(−)- and (''R'')-(+)-1,1{{prime}}-bi-2-naphthol"] {{Webarchive|url=https://web.archive.org/web/20050418112746/http://www.orgsyn.org/orgsyn/prep.asp?prep=CV9P0077 |date=2005-04-18 }}, Romas J. Kazlauskas in [[Organic Syntheses]], Coll. Vol. 9, p.77; Vol. 70, p.60</ref> The third method employs [[High-performance liquid chromatography|HPLC]] with chiral stationary phases.<ref>{{cite journal|last1 = Landek|first1 = G.|last2 = Vinković|first2 = M.|last3 = Kontrec|first3 = D.|last4 = Vinković|first4 = V.|year = 2006| title = Influence of mobile phase and temperature on separation of 1,1{{prime}}-binaphthyl-2,2{{prime}}-diol enantiomers with brush type chiral stationary phases derived from L-leucine|journal = Chromatographia|volume = 64|issue = 7–8|pages = 469–473|doi = 10.1365/s10337-006-0041-5| s2cid=95785346 }}</ref> |
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In another method BINOL is reacted with the [[acid chloride]] pentanoyl chloride to obtain the di-[[ester compound]]. The enzyme [[cholesterol]] [[esterase]] is then added in the form of [[bovine]] [[pancreas]] acetone powder which is able to [[Hydrolysis|hydrolyse]] the (''S'')-di-ester but not the (''R'')-di-ester.<ref name="orgsyn" /> The (''R'')-dipentanoate is hydrolysed in a second step with [[sodium methoxide]].<ref name="orgsyn2">[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv9p0077 "(S)-(−)- AND (R)-(+)-1,1'-BI-2-NAPHTHOL"], Romas J. Kazlauskas in [[Organic Syntheses]], Coll. Vol. 9, p.77; Vol. 70, p.60</ref> |
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[[File:Chiral phosphoric acid.png|thumb|left|162px|Structure of a [[chiral phosphoric acid]] derived from BINOL.<ref>{{cite journal |doi=10.1021/cr5001496|title=Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates|year=2014|last1=Parmar|first1=Dixit|last2=Sugiono|first2=Erli|last3=Raja|first3=Sadiya|last4=Rueping|first4=Magnus|journal=Chemical Reviews|volume=114|issue=18|pages=9047–9153|pmid=25203602|doi-access=free}}</ref>]] |
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Aside from the starting materials derived directly from the [[Chiral pool synthesis|chiral pool]], (''R'')- and (''S'')-BINOL in high enantiopurity (>99% [[enantiomeric excess]]) are two of the most inexpensive sources of chirality for organic synthesis, costing less than US$0.60 per gram when purchased in bulk from chemical suppliers.<ref>{{Cite journal|last1=Yang|first1=Jin-Fei|last2=Wang|first2=Rong-Hua|last3=Wang|first3=Yin-Xia|last4=Yao|first4=Wei-Wei|last5=Liu|first5=Qi-Sheng|last6=Ye|first6=Mengchun|date=2016-10-11|title=Ligand-Accelerated Direct C−H Arylation of BINOL: A Rapid One-Step Synthesis of Racemic 3,3{{prime}}-Diaryl BINOLs|journal=Angewandte Chemie International Edition|language=en|volume=55|issue=45|pages=14116–14120|doi=10.1002/anie.201607893|pmid=27726256 |issn=1433-7851}}</ref> As a consequence, it serves as an important starting material for other sources of chirality for stereoselective synthesis, both stoichiometric and substoichiometric (catalytic). |
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Many important chiral ligands are constructed from the binaphthyl scaffold and ultimately derived from BINOL as a starting material, [[BINAP]] being one of the most well known and important. |
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Third method employs [[High-performance liquid chromatography|HPLC]] with chiral stationary phases.<ref> |
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{{cite journal |
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| last = Landek |
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| first = G. |
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| coauthors = Vinković M., Kontrec D. and Vinković V. |
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| year = 2006 |
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| title = Influence of mobile phase and temperature on separation of 1,1 '-binaphthyl-2,2 '-diol enantiomers with brush type chiral stationary phases derived from L-leucine |
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| journal = Chromatographia |
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| volume = 64 |
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| pages = 469–473 |
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| doi = 10.1365/s10337-006-0041-5 |
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}} |
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</ref> |
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⚫ | The compound aluminium lithium bis(binaphthoxide) (ALB) is prepared by reaction of BINOL with [[lithium aluminium hydride]].<ref>''A practical large-scale synthesis of enantiomerically pure 3-[bis(methoxycarbonyl)methyl]cyclohexanone via catalytic asymmetric Michael reaction'' [[Tetrahedron (journal)|Tetrahedron]], Volume 58, Issue 13, 25 March '''2002''', Pages 2585–2588 Youjun Xu, Ken Ohori, Takashi Ohshima, Masakatsu Shibasaki {{doi|10.1016/S0040-4020(02)00141-2}}</ref> In a different stoichiometric ratio (1:1 BINOL/LiAlH<sub>4</sub> instead of 2:1), the chiral reducing agent BINAL (lithium dihydrido(binaphthoxy)aluminate) is produced.<ref>{{Citation|last1=Gopalan|first1=Aravamudan S.|title=Lithium Aluminum Hydride-2,2{{prime}}-Dihydroxy-1,1{{prime}}-binaphthyl|date=2001-04-15|encyclopedia=Encyclopedia of Reagents for Organic Synthesis|publisher=John Wiley & Sons, Ltd|language=en|doi=10.1002/047084289x.rl041|isbn=0471936235|last2=Jacobs|first2=Hollie K.}}</ref> |
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Many variations of BINOL exist, [[BINAP]] being one of them. |
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⚫ | The compound |
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It has been employed in an [[asymmetric Michael reaction]] with [[cyclohexenone]] and [[dimethyl malonate]]: |
It has been employed in an [[asymmetric Michael reaction]] with [[cyclohexenone]] and [[dimethyl malonate]]: |
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:[[File:AsymmetricMichael Shibasaki 2002.svg|343px |
:[[File:AsymmetricMichael Shibasaki 2002.svg|343px]] |
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==See also== |
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* [[Shibasaki catalysts]] |
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==References== |
==References== |
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{{Reflist}} |
{{Reflist}} |
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{{DEFAULTSORT:Bi-2-Naphthol, 1,1'-}} |
{{DEFAULTSORT:Bi-2-Naphthol, 1, 1'-}} |
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[[Category: |
[[Category:Naphthols]] |
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[[Category:Dimers (chemistry)]] |
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[[nl:1,1'-bi-2-naftol]] |
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[[ja:1,1'-ビ-2-ナフトール]] |
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[[pt:1,1'-Bi-2-naftol]] |