Editing BINAP

{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 435068880
| ImageFile = BINAP Enantiomers Structural Formulae V.1.svg
| ImageSize = 250
| PIN = ([1,1′-Binaphthalene]-2,2′-diyl)bis(diphenylphosphane)
| OtherNames = BINAP
|Section1={{Chembox Identifiers
| CASNo = 76189-55-4
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo_Comment = (''R'')
| CASNo1 = 76189-56-5
| CASNo1_Ref = {{cascite|correct|CAS}}
| CASNo1_Comment = (''S'')
| PubChem = 634876
| PubChem_Comment = (+)
| EC_number = 616-304-7
619-338-0
616-305-2
918-620-3
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 4F1X2F8NA3
| UNII_Comment = (''R'')
| UNII1_Ref = {{fdacite|correct|FDA}}
| UNII1 = OX12238KWH
| UNII1_Comment = (''S'')
| ChEMBL = 1275990
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| ChemSpiderID = 551072
| ChemSpiderID_Comment = (Rac)
| SMILES = c1ccc(cc1)P(c2ccccc2)c3ccc4ccccc4c3c5c6ccccc6ccc5P(c7ccccc7)c8ccccc8
| SMILES_Comment = (Rac)
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI = 1S/C44H32P2/c1-5-19-35(20-6-1)45(36-21-7-2-8-22-36)41-31-29-33-17-13-15-27-39(33)43(41)44-40-28-16-14-18-34(40)30-32-42(44)46(37-23-9-3-10-24-37)38-25-11-4-12-26-38/h1-32H
| StdInChI_Comment = (Rac)
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = MUALRAIOVNYAIW-UHFFFAOYSA-N
  }}
|Section2={{Chembox Properties
| C=44 | H=32 | P=2
| Appearance = Colorless solid
| Density =
| MeltingPtC = 239 to 241
| MeltingPt_notes = (''R'')<br>238–240&nbsp;°C (''S'')
| BoilingPt = 
| Solubility = organic solvents
  }}
|Section3={{Chembox Hazards
| MainHazards = 
| FlashPt = 
| AutoignitionPt = 
| GHSPictograms = {{GHS07}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|315|319|335|413}}
| PPhrases = {{P-phrases|261|264|271|273|280|302+352|304+340|305+351+338|312|321|332+313|337+313|362|403+233|405|501}}
 }}
}}

[[Image:BINAP 3D.png|thumb|right|Ball and stick model of BINAP viewed as above]]

'''BINAP''' (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is an [[organophosphorus compound]].  This [[Optical isomerism|chiral]] [[diphosphines|diphosphine]] [[ligand]] is widely used in [[chiral synthesis|asymmetric synthesis]].  It consists of a pair of 2-diphenylphosphino[[naphthalene|naphthyl]] groups linked at the 1 and 1′ positions.  This [[C2-Symmetric ligands|C<sub>2</sub>-symmetric framework]] lacks a [[stereocenter|stereogenic atom]], but has [[axial chirality]] due to restricted rotation ([[atropisomer]]ism). The barrier to [[racemization]] is high due to [[steric hindrance]], which limits rotation about the bond linking the naphthyl rings.  The [[dihedral angle]] between the naphthyl groups is approximately 90°.  The natural [[bite angle]] is 93°.<ref name="vanLeeuwen">{{cite journal |last1=Birkholz (née Gensow) |first1=Mandy-Nicole |last2=Freixa |first2=Zoraida |last3=van Leeuwen |first3=Piet W. N. M. |title=Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions |journal=Chemical Society Reviews |date=2009 |volume=38 |issue=4 |pages=1099–1118 |doi=10.1039/B806211K |pmid=19421583}}</ref>

==Use as ligand in asymmetric catalysis==
BINAP is used in [[organic synthesis]] for [[enantioselective]] transformations catalyzed by its [[complex (chemistry)|complexes]] of [[ruthenium]], [[rhodium]], and [[palladium]].<ref>{{cite journal |last=Kitamura |first=Masato |author2=M. Tokunaga |author3=T. Ohkuma |author4=R. Noyori  |year=1998 |title=Asymmetric hydrogenation of 3-oxo carboxylates using BINAP-ruthenium complexes |journal= [[Org. Synth.]] |volume=9 |pages=589 |url=http://www.orgsynth.org/orgsyn/prep.asp?prep=cv9p0589}}</ref> As pioneered by [[Ryōji Noyori]] and his co-workers, rhodium complexes of BINAP are useful for the synthesis of (–)-[[menthol]].<ref>{{cite journal |last=Akutagawa |first=S |year=1992 |title=A practical synthesis of (−)-menthol with the Rh-BINAP catalyst |journal= [[Chirality Ind.]] |pages=313–323}}</ref><ref>{{cite journal |last=Kumobayashi |first=Hidenori |author2=Sayo, Noboru |author3=Akutagawa, Susumu |author4=Sakaguchi, Toshiaki |author5= Tsuruta, Haruki  |year=1997 |title=Industrial asymmetric synthesis by use of metal-BINAP catalysts |journal= [[Nippon Kagaku Kaishi]] |volume=12 |issue=12 |pages=835–846|doi=10.1246/nikkashi.1997.835 |doi-access=free }}</ref>

[[Silver]] complexes are also important; BINAP-[[Silver(I) fluoride|AgF]] can be used to [[stereoselectivity|enantioselectively]] protonate [[silyl enol ether]]s.<ref>{{cite journal|last1=Yanagisawa|first1=Akira|last2=Touge|first2=Taichiro|last3=Takayoshi|first3=Arai|title=Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap⋅AgF Complex|journal=Angewandte Chemie International Edition|date=2005|volume=44|issue=10|pages=1546–8|doi=10.1002/anie.200462325|pmid=15645475 }}</ref>

Subsequent studies revealed that related [[diphosphine]]s with a narrower dihedral angle between the aromatic faces give catalysts that are more enantioselective. One such ligand is [[SEGPHOS]].<ref>{{cite journal | vauthors=Shimizu H, Nagasaki I, Matsumura K, Sayo N, Saito T  | title = Developments in Asymmetric Hydrogenation from an Industrial Perspective | year = 2007 | journal = [[Acc. Chem. Res.]] | volume = 40 | issue = 12| pages = 1385–1393 | doi = 10.1021/ar700101x | pmid = 17685581}}</ref>

==Preparation==
BINAP is prepared from [[1,1'-Bi-2-naphthol|BINOL]]<ref>{{cite web |url=http://www.rhodia-phosphines.com/docs/Rhodia.pdf |title=BINAP: An industrial approach to manufacture |accessdate=2008-10-20 |publisher=[[Rhodia (company)|Rhodia]]}}</ref><ref>{{OrgSynth |last=Cai |first=Dongwei |author2=J. F. Payack |author3=D. R. Bender |author4=D. L. Hughes |author5=T. R. Verhoeven |author6=P. J. Reider |year=1999 |title=(''R'')-(+)- and (''S'')-(−)-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP)|volume=76 |pages=6|prep=v76p0006}}</ref> via its bis[[triflate]] derivatives. Both the (''R'')- and (''S'')-[[enantiomer]]s, as well as the racemate, are commercially available. One of the wide applications include chemoselective hydrogenation, where BINAP is conjugated to rhodium.

==Further reading==
*{{cite journal |doi=10.1021/cr040652w |title=Modified BINAP: The How and the Why |date=2005 |last1=Berthod |first1=Mikaël |last2=Mignani |first2=Gérard |last3=Woodward |first3=Gary |last4=Lemaire |first4=Marc |journal=Chemical Reviews |volume=105 |issue=5 |pages=1801–1836 |pmid=15884790 }}
*{{cite journal |doi=10.1021/cr4003243 |title=Electron-Deficient Diphosphines: The Impact of DIFLUORPHOS in Asymmetric Catalysis |date=2014 |last1=Genet |first1=Jean-Pierre |last2=Ayad |first2=Tahar |last3=Ratovelomanana-Vidal |first3=Virginie |journal=Chemical Reviews |volume=114 |issue=5 |pages=2824–2880 |pmid=24517862 }}
*{{cite journal |doi=10.1021/cr9900230 |title=Non-Symmetrically Substituted 1,1'-Binaphthyls in Enantioselective Catalysis |date=2003 |last1=Kočovský |first1=Pavel |last2=Vyskočil |first2=Štěpán |last3=Smrčina |first3=Martin |journal=Chemical Reviews |volume=103 |issue=8 |pages=3213–3246 |pmid=12914496 }}
*{{cite journal |doi=10.1021/acs.chemrev.6b00564 |title=Asymmetric Hydrogenation of Nonaromatic Cyclic Substrates |date=2016 |last1=Zhang |first1=Zhenfeng |last2=Butt |first2=Nicholas A. |last3=Zhang |first3=Wanbin |journal=Chemical Reviews |volume=116 |issue=23 |pages=14769–14827 |pmid=27960269 }}
*{{cite journal |doi=10.1021/acs.chemrev.9b00682 |title=Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis |date=2020 |last1=Clevenger |first1=Andrew L. |last2=Stolley |first2=Ryan M. |last3=Aderibigbe |first3=Justis |last4=Louie |first4=Janis |journal=Chemical Reviews |volume=120 |issue=13 |pages=6124–6196 |pmid=32491839 |s2cid=219311508 }}

== References ==
{{reflist}}

{{DEFAULTSORT:Binap}}
[[Category:Diphosphines]]