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'''Tris(2,4,6-trimethoxyphenyl)phosphine''' ('''TTMPP''') is a large tri[[aryl]] [[organophosphine]] whose strong [[Lewis base|Lewis-basic]] properties make it useful as an [[organocatalyst]] for several types of [[chemical reaction]]s.
'''Tris(2,4,6-trimethoxyphenyl)phosphine''' ('''TTMPP''') is a large tri[[aryl]] [[organophosphine]] whose strong [[Lewis base|Lewis-basic]] properties make it useful as an [[organocatalyst]] for several types of [[chemical reaction]]s.


==Reactions==
It removes the [[trimethylsilyl group]] from [[ketene]] silyl [[acetal]]s (the [[enol ether]] of [[ester]]s) to give [[enolate]]s that can then act as strong [[nucleophile]]s. It thus serves as a [[catalyst]] for [[Mukaiyama aldol reaction]]s<ref>{{cite journal |title= Phosphine catalyzed aldol reaction between ketene silyl acetals and aldehydes: nucleophilic O–Si and C–Si bond cleavage by phosphines |first1= Satoru |last1= Matsukawa |first2= Naoko |last2= Okano |first3= Tsuneo |last3= Imamoto |journal= Tetrahedron Letters |volume= 41 |issue= 1 |year= 2000 |pages= 103–107 |doi= 10.1016/S0040-4039(99)02014-6 }}</ref> and group-transfer [[chain-growth polymerization]] reactions.<ref>{{cite journal |title= Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) as Potent Organocatalyst for Group Transfer Polymerization of Alkyl (Meth)acrylates |first1= Maréva |last1= Fevre |first2= Joan |last2= Vignolle |first3= Valérie |last3= Heroguez |first4= Daniel |last4= Taton |journal= Macromolecules |year= 2012 |volume= 45 |issue= 19 |pages =7711–7718 |doi= 10.1021/ma301412z|bibcode= 2012MaMol..45.7711F }}</ref>


As a [[Brønsted base]], it can deprotonate various [[Alcohol (chemistry)|alcohol]]s, giving nucleophilic [[alkoxide]]s that can undergo [[Michael addition reaction]]s.<ref>{{cite journal |title= Tris(2,4,6-trimethoxyphenyl)phosphine – a Lewis base able to compete with phosphazene bases in catalysing oxa-Michael reactions |first1= Susanne M. |last1= Fischer |first2= Petra |last2= Kaschnitz |first3= Christian |last3= Slugov |journal= Catalysis Science & Technology |year= 2022 |volume= 12 |issue= 20 |pages= 6204–6212 |doi= 10.1039/D2CY01335E |doi-access= free }}</ref>
TTMPP removes the [[trimethylsilyl group]] from [[ketene]] silyl [[acetal]]s (the [[enol ether]] of [[ester]]s) to give [[enolate]]s that can then act as strong [[nucleophile]]s. It thus serves as a [[catalyst]] for [[Mukaiyama aldol reaction]]s<ref>{{cite journal |title= Phosphine catalyzed aldol reaction between ketene silyl acetals and aldehydes: nucleophilic O–Si and C–Si bond cleavage by phosphines |first1= Satoru |last1= Matsukawa |first2= Naoko |last2= Okano |first3= Tsuneo |last3= Imamoto |journal= Tetrahedron Letters |volume= 41 |issue= 1 |year= 2000 |pages= 103–107 |doi= 10.1016/S0040-4039(99)02014-6 }}</ref> and group-transfer [[chain-growth polymerization]] reactions.<ref>{{cite journal |title= Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) as Potent Organocatalyst for Group Transfer Polymerization of Alkyl (Meth)acrylates |first1= Maréva |last1= Fevre |first2= Joan |last2= Vignolle |first3= Valérie |last3= Heroguez |first4= Daniel |last4= Taton |journal= Macromolecules |year= 2012 |volume= 45 |issue= 19 |pages =7711–7718 |doi= 10.1021/ma301412z|bibcode= 2012MaMol..45.7711F }}</ref>


It can act as a Michael nucleophile itself to catalyze [[Baylis–Hillman reaction]]s.<ref>{{cite journal |last1=Trofimov |first1=Alexander |last2=Gevorgyan |first2=Vladimir |title=Sila-Morita−Baylis−Hillman Reaction of Arylvinyl Ketones: Overcoming the Dimerization Problem |journal=[[Organic Letters]] |date=2009 |volume=11 |issue=1 |pages=253–255 |doi=10.1021/ol8026522|pmid=19055398 }}</ref>
As a [[Brønsted base]], TTMPP can deprotonate various [[Alcohol (chemistry)|alcohol]]s, giving nucleophilic [[alkoxide]]s that can undergo [[Michael addition reaction]]s.<ref>{{cite journal |title= Tris(2,4,6-trimethoxyphenyl)phosphine – a Lewis base able to compete with phosphazene bases in catalysing oxa-Michael reactions |first1= Susanne M. |last1= Fischer |first2= Petra |last2= Kaschnitz |first3= Christian |last3= Slugov |journal= Catalysis Science & Technology |year= 2022 |volume= 12 |issue= 20 |pages= 6204–6212 |doi= 10.1039/D2CY01335E |doi-access= free }}</ref>

TTMPP can act as a Michael nucleophile itself to catalyze [[Baylis–Hillman reaction]]s.<ref>{{cite journal |last1=Trofimov |first1=Alexander |last2=Gevorgyan |first2=Vladimir |title=Sila-Morita−Baylis−Hillman Reaction of Arylvinyl Ketones: Overcoming the Dimerization Problem |journal=[[Organic Letters]] |date=2009 |volume=11 |issue=1 |pages=253–255 |doi=10.1021/ol8026522|pmid=19055398 }}</ref>

==Applications==
TTMPP is used as a ligand to form [[palladium-phosphine catalyst]]s which are more reactive than [[triphenylphosphine]]-based catalysts.<ref name="1995 Suzuki review">{{cite journal |last1=Miyaura |first1=Norio |author1-link=Norio Miyaura |last2=Suzuki |first1=Akira |author2-link=Akira Suzuki |title=Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. |journal=[[Chemical Reviews]] |year=1995 |volume=95 |issue=7 |pages=2457–2483 |doi=10.1021/cr00039a007}}</ref>


== References ==
== References ==

Revision as of 19:27, 21 March 2024

Tris(2,4,6-trimethoxyphenyl)phosphine
Names
IUPAC name
Tris(2,4,6-trimethoxyphenyl)phosphane
Other names
  • Tris(2,4,6-trimethoxyphenyl)phosphine
  • TTMPP
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 811-745-3
  • InChI=1S/C27H33O9P/c1-28-16-10-19(31-4)25(20(11-16)32-5)37(26-21(33-6)12-17(29-2)13-22(26)34-7)27-23(35-8)14-18(30-3)15-24(27)36-9/h10-15H,1-9H3
    Key: JQKHNBQZGUKYPX-UHFFFAOYSA-N
  • COC1=CC(=C(C(=C1)OC)P(C2=C(C=C(C=C2OC)OC)OC)C3=C(C=C(C=C3OC)OC)OC)OC
Properties
C27H33O9P
Molar mass 532.526 g·mol−1
Melting point 79–81 °C (174–178 °F; 352–354 K)
Boiling point 360 or 377 °C (680 or 711 °F; 633 or 650 K)[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) is a large triaryl organophosphine whose strong Lewis-basic properties make it useful as an organocatalyst for several types of chemical reactions.

Reactions

TTMPP removes the trimethylsilyl group from ketene silyl acetals (the enol ether of esters) to give enolates that can then act as strong nucleophiles. It thus serves as a catalyst for Mukaiyama aldol reactions[2] and group-transfer chain-growth polymerization reactions.[3]

As a Brønsted base, TTMPP can deprotonate various alcohols, giving nucleophilic alkoxides that can undergo Michael addition reactions.[4]

TTMPP can act as a Michael nucleophile itself to catalyze Baylis–Hillman reactions.[5]

Applications

TTMPP is used as a ligand to form palladium-phosphine catalysts which are more reactive than triphenylphosphine-based catalysts.[6]

References

  1. ^ Various chemical catalogs give one or the other value (see ChemSpider for collected list)
  2. ^ Matsukawa, Satoru; Okano, Naoko; Imamoto, Tsuneo (2000). "Phosphine catalyzed aldol reaction between ketene silyl acetals and aldehydes: nucleophilic O–Si and C–Si bond cleavage by phosphines". Tetrahedron Letters. 41 (1): 103–107. doi:10.1016/S0040-4039(99)02014-6.
  3. ^ Fevre, Maréva; Vignolle, Joan; Heroguez, Valérie; Taton, Daniel (2012). "Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) as Potent Organocatalyst for Group Transfer Polymerization of Alkyl (Meth)acrylates". Macromolecules. 45 (19): 7711–7718. Bibcode:2012MaMol..45.7711F. doi:10.1021/ma301412z.
  4. ^ Fischer, Susanne M.; Kaschnitz, Petra; Slugov, Christian (2022). "Tris(2,4,6-trimethoxyphenyl)phosphine – a Lewis base able to compete with phosphazene bases in catalysing oxa-Michael reactions". Catalysis Science & Technology. 12 (20): 6204–6212. doi:10.1039/D2CY01335E.
  5. ^ Trofimov, Alexander; Gevorgyan, Vladimir (2009). "Sila-Morita−Baylis−Hillman Reaction of Arylvinyl Ketones: Overcoming the Dimerization Problem". Organic Letters. 11 (1): 253–255. doi:10.1021/ol8026522. PMID 19055398.
  6. ^ Miyaura, Akira; Suzuki (1995). "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds". Chemical Reviews. 95 (7): 2457–2483. doi:10.1021/cr00039a007.
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