: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)
238–240 °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

BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is an organophosphorus compound. This chiral diphosphine ligand is widely used in asymmetric synthesis. It consists of a pair of 2-diphenylphosphinonaphthyl groups linked at the 1 and 1′ positions. This C₂-symmetric framework lacks a stereogenic atom, but has axial chirality due to restricted rotation (atropisomerism). 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°.{{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}}

Use as ligand in asymmetric catalysis

BINAP is used in organic synthesis for enantioselective transformations catalyzed by its complexes of ruthenium, rhodium, and palladium.{{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}} As pioneered by Ryōji Noyori and his co-workers, rhodium complexes of BINAP are useful for the synthesis of (–)-menthol.{{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}}{{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 }}

Silver complexes are also important; BINAP-AgF can be used to enantioselectively protonate silyl enol ethers.{{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 }}

Subsequent studies revealed that related diphosphines with a narrower dihedral angle between the aromatic faces give catalysts that are more enantioselective. One such ligand is SEGPHOS.{{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}}

Preparation

BINAP is prepared from BINOL{{cite web |url=http://www.rhodia-phosphines.com/docs/Rhodia.pdf |title=BINAP: An industrial approach to manufacture |accessdate=2008-10-20 |publisher=Rhodia}}{{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}} via its bistriflate derivatives. Both the (R)- and (S)-enantiomers, as well as the racemate, are commercially available. One of the wide applications include chemoselective hydrogenation, where BINAP is conjugated to rhodium.

References

Category:Diphosphines

:BINAP

Use as ligand in asymmetric catalysis

Preparation

Further reading

References