Dialkylbiaryl phosphine ligands

Last updated

Dialkylbiaryl phosphine ligands are phosphine ligands that are used in homogeneous catalysis. They have proved useful in Buchwald-Hartwig amination and etherification reactions as well as Negishi cross-coupling, Suzuki-Miyaura cross-coupling, and related reactions. [1] In addition to these Pd-based processes, their use has also been extended to transformations catalyzed by nickel, [2] gold, [3] [4] [5] silver, [6] copper, [7] rhodium, [8] [9] and ruthenium, [10] [11] among other transition metals. [12]

Contents

History

Dialkylbiaryl phosphine ligands were first described by Stephen L. Buchwald in 1998 for applications in palladium-catalyzed coupling reactions to form carbon-nitrogen and carbon-carbon bonds. [13] Before their development, use of first- or second-generation phosphine ligands for Pd-catalyzed C-N bond-forming cross-coupling (e.g., tris(o-tolyl)phosphine and BINAP, respectively) necessitated harsh conditions, and the scope of the transformation was severely limited. The Suzuki-Miyaura and Negishi cross-coupling reactions were typically performed with Pd(PPh3)4 as catalyst and were mostly limited to aryl bromides and iodides at elevated temperatures, while the widely available aryl chlorides were unreactive. Dialkylbiaryl phosphine ligands are sometimes referred to as the "Buchwald ligands." [14]

General features

One pot synthesis of dialkylbiaryl phosphine ligands One pot synthesis dialkylbiaryl phosphine ligands.svg
One pot synthesis of dialkylbiaryl phosphine ligands

Dialkylbiaryl phosphine ligands are air-stable solids. Many are available commercially. They often can be synthesized in from inexpensive starting materials. One pot protocols have been conducted on >10 kg scales. [15] [16]

Structural features of the dialkylbiarylphosphines and their impact on the efficacy of catalysts using these ligands Structural features of the dialkylbiarylphosphines and their impact on the efficacy of catalysts using these ligands.png
Structural features of the dialkylbiarylphosphines and their impact on the efficacy of catalysts using these ligands

Their enhanced catalytic activity over other ligands in palladium-catalyzed coupling reactions have been attributed to their electron-richness, steric bulk, and some special structural features. In particular, cyclohexyl, t-butyl, and adamantyl groups on the phosphorus are used for this purpose as bulky, electron-donating substituents. The lower ring of the biphenyl system, ortho to the phosphino group, is also a key structural feature. Numerous crystallographic studies have indicated that it behaves as a hemilabile ligand and is believed to play a role in stabilizing the highly reactive, formally 12-electron L–Pd0 intermediate during the catalytic cycle. 2,6-Substitution on the lower ring minimizes catalyst decomposition via Pd-mediated C-H activation of these positions. Extensive experimentation by the Buchwald group has shown that further minor changes to the structure of these ligands can dramatically alter their catalytic activity in cross coupling reactions with different substrates. This has led to the evolution of multiple ligands that are tailored for specific transformations. [17] By providing a means of generating the postulated catalytically active L–Pd0 species under mild conditions (room temperature or lower in many cases), the development of several generations of base-activated, cyclopalladated precatalysts have further broadened the applicability of the ligands and simplified their use. [18] [19]

Common Dialkylbiaryl phosphine ligands

DavePhos

DavePhos DavePhos.svg
DavePhos

DavePhos, the first reported dialkylbiaryl phosphine ligand, was initially used in Pd-catalyzed Suzuki-Miyaura cross-coupling reactions as well as Buchwald-Hartwig aminations. [20] Complexes of this ligand also catalyze a wide array of reactions, including the arylation of ketones [21] and esters, [22] borylation of aryl chlorides, [23] and the arylation of indoles. [24]

Many modified versions of DavePhos have been synthesized. t-BuDavePhos has been shown to be an even more reactive variant of DavePhos in the room temperature Suzuki-Miyaura coupling of aryl bromides and chlorides. [25] The biphenyl equivalent (PhDavePhos) is also available.

JohnPhos

JohnPhos JohnPhos.svg
JohnPhos

JohnPhos supports the Pd-catalyzed Suzuki-Miyaura reactions with aryl bromides and chlorides. [26] It tolerates hindered substrates and operates at room temperature with low catalyst loading. This ligand has been utilized in multiple reactions including the amination of a range of aryl halides and triflates [27] [28] as well as the arylation of thiophenes. [29]

MePhos

MePhos MePhos.svg
MePhos

Like DavePhos and JohnPhos, MePhos is competent in the Pd-catalyzed Suzuki-Miyaura coupling. [30] It can also form the active catalyst in the formation of aryl ketones. [31] Variants of this ligand, including t-BuMePhos, are also commercially available.

The Pd2(dba)3/MePhos catalytic system has been applied to late stage Suzuki cross couplings. This reaction has been conducted on a kilogram scale, and no specific palladium-removal treatment was required as the excess imidazole present in the final amide coupling step coordinated to the Pd and generated a removable byproduct. [32]

Amgen kilogram-acale aynthesis of p38 MAP kinase inhibitor candidate Amgen Kilogram-Scale Synthesis of p38 MAP Kinase Inhibitor Candidate.png
Amgen kilogram-acale aynthesis of p38 MAP kinase inhibitor candidate

XPhos

XPhos XPhos.svg
XPhos

XPhos supports Pd-based catalysts for amination and amidation of arylsulfonates and aryl halides. [33] XPhos has also been used in the Pd-catalyzed borylation of aryl and heteroaryl chlorides [34]

Modified versions of XPhos, he more hindered t-BuXPhos and Me4tButylXPhos, have been employed in the formation of diaryl ethers. [35] Incorporation of a sulfonate group at the 4-position allows this ligand to be used for Sonogashira couplings in aqueous biphasic solvents. [36]

SPhos

SPhos SPhos.svg
SPhos

SPhos has proven effective in Pd-catalyzed Suzuki-Miyaura coupling reactions. [37] This ligand enables the cross-coupling of heteroaryl, electron-rich and electron-poor aryl, and vinylboronic acids with a variety of aryl and heteroaryl halides under mild reaction conditions. SPhos has also been used in the Pd-catalyzed borylation of aryl and heteroaryl chlorides. [38]

3-Sulfonate variants of sSPhos have been used in Suzuki-Miyaura couplings in aqueous media. [39] SPhos was used in the 8 step total synthesis of (±)-geigerin. [40]

Synthesis of geigerin through Suzuki-Miyaura Coupling Synthesis of geigerin through Suzuki-Miyaura Coupling.png
Synthesis of geigerin through Suzuki-Miyaura Coupling

RuPhos

RuPhos RuPhos.svg
RuPhos

RuPhos has proven effective for Pd-catalyzed Negishi coupling of organozincs with aryl halides. [41] This ligands tolerates hindered substrates as well as a wide range of functional groups. Its complexes also catalyze the trifluoromethylation of aryl chlorides [42] and aminations of aryl halides. [43]

BrettPhos

BrettPhos BrettPhos.svg
BrettPhos

BrettPhos has been evaluated for the Pd-catalyzed amination of aryl mesylates and aryl halides. [44] Pd-BrettPhos complexes catalyze the coupling of weak nucleophiles with aryl halides. Such catalysts are selective for the monoarylation of primary amines. Other applications of BrettPhos in catalysis include trifluoromethylation of aryl chlorides, [45] the formation of aryl trifluoromethyl sulfides, [46] and Suzuki-Miyaura cross-couplings. [47]

Pd- t-BuBrettPhos complexes catalyze the conversion of aryl triflates and aryl bromides to aryl fluorides [48] as well as the synthesis of aromatic nitro compounds. [49] The bulky AdBrettPhos can be used in the amidation of five-membered heterocyclic halides that contain multiple heteroatoms (such as haloimidazoles and halopyrazoles). [50]

CPhos

CPhos CPhos2.png
CPhos

CPhos has been used as a ligand in the Pd-catalyzed synthesis of 3-cyclopentylindole derivatives, [51] dihydrobenzofurans, [52] and trans-bicyclic sulfamides. [53] It has also been used to synthesize palladacycle precatalysts for Negishi coupling of secondary alkylzinc reagents with aryl halides. [54] [55] [56]

AlPhos

AlPhos AlPhos.png
AlPhos

AlPhos allows for the mild Pd-catalyzed fluorination of aryl- and heteroaryl triflates. [57] Reported in 2015, this ligand has been used for Buchwald-Hartwig cross-coupling reactions and synthesizing highly regioselective aryl fluorides through Pd-catalyzed fluorination of various activated aryl and heteroaryl triflates and bromides. [58] [59] Its palladium complexes have also been used to prepare aryl thioethers by C–S cross-coupling of thiols with aromatic electrophiles. [60]

Oxidative addition complex

Oxidative Addition Complex.png

Many Pd-catalyzed cross coupling reactions involve oxidative addition to form Pd(II) derivatives called oxidative addition complexes (OAC). The resulting L–PdII(Ar)X OAC is electrophilic such that it reacts with a nucleophile and forms C–C and C–heteroatom bonds, after reductive elimination. [61] Such PdIIOACs have been used as precatalysts. [62] OACs exhibit stability, which allows reactions to proceed under mild conditions. They have been applied to bioconjugation. [63] For example, RuPhos and SPhos have been used as ligands for Pd-mediated cysteine arylation, and the use of BrettPhos and t-BuBrettPhos are critical for lysine arylation. [64] [65] [66] [67]

See also

Related Research Articles

The Suzuki reaction or Suzuki coupling is an organic reaction that uses a palladium complex catalyst to cross-couple a boronic acid to an organohalide. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their contribution to the discovery and development of noble metal catalysis in organic synthesis. This reaction is sometimes telescoped with the related Miyaura borylation; the combination is the Suzuki–Miyaura reaction. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls.

<span class="mw-page-title-main">Transition metal pincer complex</span>

In chemistry, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly to three adjacent coplanar sites in a meridional configuration. The inflexibility of the pincer-metal interaction confers high thermal stability to the resulting complexes. This stability is in part ascribed to the constrained geometry of the pincer, which inhibits cyclometallation of the organic substituents on the donor sites at each end. In the absence of this effect, cyclometallation is often a significant deactivation process for complexes, in particular limiting their ability to effect C-H bond activation. The organic substituents also define a hydrophobic pocket around the reactive coordination site. Stoichiometric and catalytic applications of pincer complexes have been studied at an accelerating pace since the mid-1970s. Most pincer ligands contain phosphines. Reactions of metal-pincer complexes are localized at three sites perpendicular to the plane of the pincer ligand, although in some cases one arm is hemi-labile and an additional coordination site is generated transiently. Early examples of pincer ligands were anionic with a carbanion as the central donor site and flanking phosphine donors; these compounds are referred to as PCP pincers.

The Negishi coupling is a widely employed transition metal catalyzed cross-coupling reaction. The reaction couples organic halides or triflates with organozinc compounds, forming carbon-carbon bonds (C-C) in the process. A palladium (0) species is generally utilized as the catalyst, though nickel is sometimes used. A variety of nickel catalysts in either Ni0 or NiII oxidation state can be employed in Negishi cross couplings such as Ni(PPh3)4, Ni(acac)2, Ni(COD)2 etc.

In organic chemistry, the Buchwald–Hartwig amination is a chemical reaction for the synthesis of carbon–nitrogen bonds via the palladium-catalyzed coupling reactions of amines with aryl halides. Although Pd-catalyzed C–N couplings were reported as early as 1983, Stephen L. Buchwald and John F. Hartwig have been credited, whose publications between 1994 and the late 2000s established the scope of the transformation. The reaction's synthetic utility stems primarily from the shortcomings of typical methods for the synthesis of aromatic C−N bonds, with most methods suffering from limited substrate scope and functional group tolerance. The development of the Buchwald–Hartwig reaction allowed for the facile synthesis of aryl amines, replacing to an extent harsher methods while significantly expanding the repertoire of possible C−N bond formations.

<span class="mw-page-title-main">1,1'-Bis(diphenylphosphino)ferrocene</span> Chemical compound

1,1′-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an organophosphorus compound commonly used as a ligand in homogeneous catalysis. It contains a ferrocene moiety in its backbone, and is related to other bridged diphosphines such as 1,2-bis(diphenylphosphino)ethane (dppe).

Bioconjugation is a chemical strategy to form a stable covalent link between two molecules, at least one of which is a biomolecule.

<span class="mw-page-title-main">Boroxine</span> 6-sided cyclic compound of oxygen and boron

Boroxine is a 6-membered heterocyclic compound composed of alternating oxygen and singly-hydrogenated boron atoms. Boroxine derivatives such as trimethylboroxine and triphenylboroxine also make up a broader class of compounds called boroxines. These compounds are solids that are usually in equilibrium with their respective boronic acids at room temperature. Beside being used in theoretical studies, boroxine is primarily used in the production of optics.

<span class="mw-page-title-main">SPhos</span> Chemical compound

SPhos is a phosphine ligand derived from biphenyl. Its palladium complexes exhibit high activity for Suzuki coupling reactions involving aryl chlorides, which are unreactive with palladium complexes of most other phosphine ligands. The ligand has convenient handling characteristics since it is air-stable.

<span class="mw-page-title-main">XPhos</span> Chemical compound

XPhos is a phosphine ligand derived from biphenyl. Its palladium complexes exhibit high activity for Buchwald-Hartwig amination reactions involving aryl chlorides and aryl tosylates. Both palladium and copper complexes of the compound exhibit high activity for the coupling of aryl halides and aryl tosylates with various amides. It is also an efficient ligand for several commonly used C–C bond-forming cross-coupling reactions, including the Negishi, Suzuki, and the copper-free Sonogashira coupling reactions. It is especially efficient and general when employed as a (2-aminobiphenyl)-cyclometalated palladium mesylate precatalyst complex, XPhos-G3-Pd, which is commercially available and stable to bench storage. The ligand itself also has convenient handling characteristics as a crystalline, air-stable solid.

Bruce H. Lipshutz is an American chemist. He is a professor at the University of California, Santa Barbara.

<span class="mw-page-title-main">Bis(triphenylphosphine)palladium chloride</span> Chemical compound

Bis(triphenylphosphine)palladium chloride is a coordination compound of palladium containing two triphenylphosphine and two chloride ligands. It is a yellow solid that is soluble in some organic solvents. It is used for palladium-catalyzed coupling reactions, e.g. the Sonogashira–Hagihara reaction. The complex is square planar. Many analogous complexes are known with different phosphine ligands.

1-Decyne is the organic compound with the formula C8H17C≡CH. It is a terminal alkyne. A colorless liquid, 1-decyne is used as a model substrate when evaluating methodology in organic synthesis. It participates in a number of classical reactions including Suzuki-Miyaura couplings, Sonogashira couplings, Huisgen cycloadditions, and borylations.

<span class="mw-page-title-main">Josiphos ligands</span>

A Josiphos ligand is a type of chiral diphosphine which has been modified to be substrate-specific; they are widely used for enantioselective synthesis. They are widely used in asymmetric catalysis.

<span class="mw-page-title-main">John P. Wolfe</span>

John Perry Wolfe is an American chemist and a professor of chemistry at the University of Michigan. He is best known for palladium-catalyzed C-C and C-N bond formation reactions. He was also one of the key scientists in the development of Buchwald ligands, one of which is appropriately named "JohnPhos" after him. Wolfe has taught at the University of Michigan since 2002.

<span class="mw-page-title-main">Catellani reaction</span>

The Catellani reaction was discovered by Marta Catellani and co-workers in 1997. The reaction uses aryl iodides to perform bi- or tri-functionalization, including C-H functionalization of the unsubstituted ortho position(s), followed a terminating cross-coupling reaction at the ipso position. This cross-coupling cascade reaction depends on the ortho-directing transient mediator, norbornene.

<span class="mw-page-title-main">Palladium–NHC complex</span>

In organometallic chemistry, palladium-NHC complexes are a family of organopalladium compounds in which palladium forms a coordination complex with N-heterocyclic carbenes (NHCs). They have been investigated for applications in homogeneous catalysis, particularly cross-coupling reactions.

Palladacycle, as a class of metallacycles, refers to complexes containing at least one carbon-palladium bond. Palladacycles are invoked as intermediates in catalytic or palladium mediated reactions. They have been investigated as pre-catalysts for homogeneous catalysis and synthesis.

Mark Stradiotto is a Canadian chemist. He is currently the Arthur B. McDonald Research Chair and the Alexander McLeod Professor of Chemistry in the Department of Chemistry at Dalhousie University.

Miyaura borylation, also known as the Miyaura borylation reaction, is a named reaction in organic chemistry that allows for the generation of boronates from vinyl or aryl halides with the cross-coupling of bis(pinacolato)diboron in basic conditions with a catalyst such as PdCl2(dppf). The resulting borylated products can be used as coupling partners for the Suzuki reaction.

Palladium forms a variety of ionic, coordination, and organopalladium compounds, typically with oxidation state Pd0 or Pd2+. Palladium(III) compounds have also been reported. Palladium compounds are frequently used as catalysts in cross-coupling reactions such as the Sonogashira coupling and Suzuki reaction.

References

  1. ↑ Surry, David S.; Buchwald, Stephen L. (2008-08-11). "Biaryl Phosphane Ligands in Palladium-Catalyzed Amination". Angewandte Chemie International Edition. 47 (34): 6338–6361. doi:10.1002/anie.200800497. ISSN   1521-3773. PMC   3517088 . PMID   18663711.
  2. ↑ Newman-Stonebraker, Samuel H.; Wang, Jason Y.; Jeffrey, Philip D.; Doyle, Abigail G. (October 2022). "Structure–Reactivity Relationships of Buchwald-Type Phosphines in Nickel-Catalyzed Cross-Couplings" (PDF). Journal of the American Chemical Society. 144 (42): 19635–19648. doi:10.1021/jacs.2c09840. PMC   10276769 . PMID   36250758. S2CID   252917338.
  3. ↑ Ferrer, Catalina; Amijs, Catelijne H. M.; Echavarren, Antonio M. (2007-02-02). "Intra- and Intermolecular Reactions of Indoles with Alkynes Catalyzed by Gold". Chemistry - A European Journal. 13 (5): 1358–1373. doi:10.1002/chem.200601324. PMID   17206736.
  4. ↑ Ferrer, Catalina; Echavarren, Antonio M. (2006-02-06). "Gold-Catalyzed Intramolecular Reaction of Indoles with Alkynes: Facile Formation of Eight-Membered Rings and an Unexpected Allenylation". Angewandte Chemie (in German). 118 (7): 1123–1127. doi:10.1002/ange.200503484. ISSN   0044-8249.
  5. ↑ López, Salomé; Herrero-Gómez, Elena; Pérez-Galán, Patricia; Nieto-Oberhuber, Cristina; Echavarren, Antonio M. (2006-09-11). "Gold(I)-Catalyzed Intermolecular Cyclopropanation of Enynes with Alkenes: Trapping of Two Different Gold Carbenes". Angewandte Chemie (in German). 118 (36): 6175–6178. doi:10.1002/ange.200602448. ISSN   0044-8249.
  6. ↑ Porcel, Susana; Echavarren, Antonio M. (2007-03-06). "Intramolecular Carbostannylation of Alkynes Catalyzed by Silver(I) Species". Angewandte Chemie. 119 (15): 2726–2730. doi:10.1002/ange.200605041.
  7. ↑ Haider, Joachim; Kunz, Klaus; Scholz, Ulrich (June 2004). "Highly Selective Copper-Catalyzed Monoarylation of Aniline". Advanced Synthesis & Catalysis. 346 (7): 717–722. doi:10.1002/adsc.200404011. ISSN   1615-4150.
  8. ↑ Dhondi, Pawan K.; Chisholm, John D. (2006-01-01). "Rhodium-Catalyzed Addition of Alkynes to Activated Ketones and Aldehydes". Organic Letters. 8 (1): 67–69. doi:10.1021/ol0525260. ISSN   1523-7060. PMID   16381569.
  9. ↑ Dhondi, Pawan K.; Carberry, Patrick; Choi, Lydia B.; Chisholm, John D. (2007-12-01). "Addition of Alkynes to Aldehydes and Activated Ketones Catalyzed by Rhodium−Phosphine Complexes". The Journal of Organic Chemistry. 72 (25): 9590–9596. doi:10.1021/jo701643h. ISSN   0022-3263. PMID   17999525.
  10. ↑ Movassaghi, Mohammad; Hill, Matthew D. (2006-11-01). "Single-Step Synthesis of Pyrimidine Derivatives". Journal of the American Chemical Society. 128 (44): 14254–14255. doi:10.1021/ja066405m. ISSN   0002-7863. PMID   17076488.
  11. ↑ Faller, J. W.; D'Alliessi, Darlene G. (2003-06-01). "Planar Chirality in Tethered η 6 :η 1 -(Phosphinophenylenearene -P )ruthenium(II) Complexes and Their Potential Use as Asymmetric Catalysts". Organometallics. 22 (13): 2749–2757. doi:10.1021/om030080q. ISSN   0276-7333.
  12. ↑ Surry, David S.; Buchwald, Stephen L. (2011). "Dialkylbiaryl phosphines in Pd-catalyzed amination: a user's guide". Chem. Sci. 2 (1): 27–50. doi:10.1039/C0SC00331J. ISSN   2041-6539. PMC   3306613 . PMID   22432049.
  13. ↑ Old, David W.; Wolfe, John P.; Buchwald, Stephen L. (September 1998). "A Highly Active Catalyst for Palladium-Catalyzed Cross-Coupling Reactions: Room-Temperature Suzuki Couplings and Amination of Unactivated Aryl Chlorides". Journal of the American Chemical Society. 120 (37): 9722–9723. doi:10.1021/ja982250+.
  14. ↑ "Buchwald Phosphine Ligands". Sigma-Aldrich. Retrieved 2023-06-08.
  15. ↑ Martin, Ruben; Buchwald, Stephen L. (18 November 2008). "Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands". Accounts of Chemical Research. 41 (11): 1461–1473. doi:10.1021/ar800036s. ISSN   0001-4842. PMC   2645945 . PMID   18620434.
  16. ↑ Kaye, Steven; Fox, Joseph M.; Hicks, Frederick A.; Buchwald, Stephen L. (31 December 2001). "The Use of Catalytic Amounts of CuCl and Other Improvements in the Benzyne Route to Biphenyl-Based Phosphine Ligands". Advanced Synthesis & Catalysis. 343 (8): 789–794. doi:10.1002/1615-4169(20011231)343:8<789::AID-ADSC789>3.0.CO;2-A. ISSN   1615-4169.
  17. ↑ Martin, Ruben; Buchwald, Stephen L. (18 November 2008). "Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands". Accounts of Chemical Research. 41 (11): 1461–1473. doi:10.1021/ar800036s. ISSN   0001-4842. PMC   2645945 . PMID   18620434.
  18. ↑ Biscoe, Mark R.; Fors, Brett P.; Buchwald, Stephen L. (2008-05-01). "A New Class of Easily Activated Palladium Precatalysts for Facile C−N Cross-Coupling Reactions and the Low Temperature Oxidative Addition of Aryl Chlorides". Journal of the American Chemical Society. 130 (21): 6686–6687. doi:10.1021/ja801137k. PMC   2587037 . PMID   18447360.
  19. ↑ Bruno, N. C.; Buchwald, S. L. (2014). Palladium Precatalysts for Cross-Coupling Reactions (PDF). The Strem Chemiker.
  20. ↑ Old, David W.; Wolfe, John P.; Buchwald, Stephen L. (September 1998). "A Highly Active Catalyst for Palladium-Catalyzed Cross-Coupling Reactions: Room-Temperature Suzuki Couplings and Amination of Unactivated Aryl Chlorides". Journal of the American Chemical Society. 120 (37): 9722–9723. doi:10.1021/ja982250+.
  21. ↑ Fox, Joseph M.; Huang, Xiaohua; Chieffi, André; Buchwald, Stephen L. (1 February 2000). "Highly Active and Selective Catalysts for the Formation of α-Aryl Ketones". Journal of the American Chemical Society. 122 (7): 1360–1370. doi:10.1021/ja993912d. ISSN   0002-7863.
  22. ↑ Moradi, Wahed A.; Buchwald, Stephen L. (2001). "Palladium-Catalyzedα-Arylation of Esters". Journal of the American Chemical Society. 123 (33): 7996–8002. doi:10.1021/ja010797+. ISSN   0002-7863. PMID   11506555.
  23. ↑ Billingsley, Kelvin L.; Barder, Timothy E.; Buchwald, Stephen L. (9 July 2007). "Palladium-Catalyzed Borylation of Aryl Chlorides: Scope, Applications, and Computational Studies". Angewandte Chemie International Edition. 46 (28): 5359–5363. doi:10.1002/anie.200701551. ISSN   1521-3773. PMID   17562550.
  24. ↑ Old, David W.; Harris, Michele C.; Buchwald, Stephen L. (1 May 2000). "Efficient Palladium-Catalyzed N-Arylation of Indoles". Organic Letters. 2 (10): 1403–1406. doi:10.1021/ol005728z. ISSN   1523-7060. PMID   10814458.
  25. ↑ Wolfe, John P.; Singer, Robert A.; Yang, Bryant H.; Buchwald, Stephen L. (1 October 1999). "Highly Active Palladium Catalysts for Suzuki Coupling Reactions". Journal of the American Chemical Society. 121 (41): 9550–9561. doi:10.1021/ja992130h. ISSN   0002-7863.
  26. ↑ Wolfe, John P.; Singer, Robert A.; Yang, Bryant H.; Buchwald, Stephen L. (1 October 1999). "Highly Active Palladium Catalysts for Suzuki Coupling Reactions". Journal of the American Chemical Society. 121 (41): 9550–9561. doi:10.1021/ja992130h. ISSN   0002-7863.
  27. ↑ Wolfe, John P.; Tomori, Hiroshi; Sadighi, Joseph P.; Yin, Jingjun; Buchwald, Stephen L. (1 February 2000). "Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates" (PDF). The Journal of Organic Chemistry. 65 (4): 1158–1174. doi:10.1021/jo991699y. ISSN   0022-3263. PMID   10814067.
  28. ↑ Surry, David S.; Buchwald, Stephen L. (11 August 2008). "Biaryl Phosphane Ligands in Palladium-Catalyzed Amination". Angewandte Chemie International Edition. 47 (34): 6338–6361. doi:10.1002/anie.200800497. ISSN   1521-3773. PMC   3517088 . PMID   18663711.
  29. ↑ Okazawa, Toru; Satoh, Tetsuya; Miura, Masahiro; Nomura, Masakatsu (1 May 2002). "Palladium-Catalyzed Multiple Arylation of Thiophenes". Journal of the American Chemical Society. 124 (19): 5286–5287. doi:10.1021/ja0259279. ISSN   0002-7863. PMID   11996567.
  30. ↑ Wolfe, John P.; Singer, Robert A.; Yang, Bryant H.; Buchwald, Stephen L. (1 October 1999). "Highly Active Palladium Catalysts for Suzuki Coupling Reactions". Journal of the American Chemical Society. 121 (41): 9550–9561. doi:10.1021/ja992130h. ISSN   0002-7863.
  31. ↑ Fox, Joseph M.; Huang, Xiaohua; Chieffi, André; Buchwald, Stephen L. (1 February 2000). "Highly Active and Selective Catalysts for the Formation of α-Aryl Ketones". Journal of the American Chemical Society. 122 (7): 1360–1370. doi:10.1021/ja993912d. ISSN   0002-7863.
  32. ↑ Thiel, Oliver; Achmatowicz, Michal; Milburn, Robert (11 June 2012). "Process Research and Development for Heterocyclic p38 MAP Kinase Inhibitors". Synlett. 23 (11): 1564–1574. doi:10.1055/s-0031-1290425. S2CID   196773656.
  33. ↑ Huang, Xiaohua; Anderson, Kevin W.; Zim, Danilo; Jiang, Lei; Klapars, Artis; Buchwald, Stephen L. (1 June 2003). "Expanding Pd-Catalyzed C−N Bond-Forming Processes: The First Amidation of Aryl Sulfonates, Aqueous Amination, and Complementarity with Cu-Catalyzed Reactions". Journal of the American Chemical Society. 125 (22): 6653–6655. doi:10.1021/ja035483w. ISSN   0002-7863. PMID   12769573.
  34. ↑ Billingsley, Kelvin L.; Barder, Timothy E.; Buchwald, Stephen L. (9 July 2007). "Palladium-Catalyzed Borylation of Aryl Chlorides: Scope, Applications, and Computational Studies". Angewandte Chemie International Edition. 46 (28): 5359–5363. doi:10.1002/anie.200701551. ISSN   1521-3773. PMID   17562550.
  35. ↑ Burgos, Carlos H.; Barder, Timothy E.; Huang, Xiaohua; Buchwald, Stephen L. (26 June 2006). "Significantly Improved Method for the Pd-Catalyzed Coupling of Phenols with Aryl Halides: Understanding Ligand Effects". Angewandte Chemie International Edition. 45 (26): 4321–4326. doi:10.1002/anie.200601253. ISSN   1521-3773. PMID   16733839.
  36. ↑ Anderson, Kevin W.; Buchwald, Stephen L. (26 September 2005). "General Catalysts for the Suzuki–Miyaura and Sonogashira Coupling Reactions of Aryl Chlorides and for the Coupling of Challenging Substrate Combinations in Water". Angewandte Chemie International Edition. 44 (38): 6173–6177. doi:10.1002/anie.200502017. ISSN   1521-3773. PMID   16097019.
  37. ↑ Walker, Shawn D.; Barder, Timothy E.; Martinelli, Joseph R.; Buchwald, Stephen L. (26 March 2004). "A Rationally Designed Universal Catalyst for Suzuki–Miyaura Coupling Processes". Angewandte Chemie International Edition. 43 (14): 1871–1876. doi:10.1002/anie.200353615. ISSN   1521-3773. PMID   15054800.
  38. ↑ Billingsley, Kelvin L.; Barder, Timothy E.; Buchwald, Stephen L. (9 July 2007). "Palladium-Catalyzed Borylation of Aryl Chlorides: Scope, Applications, and Computational Studies". Angewandte Chemie International Edition. 46 (28): 5359–5363. doi:10.1002/anie.200701551. ISSN   1521-3773. PMID   17562550.
  39. ↑ Anderson, Kevin W.; Buchwald, Stephen L. (26 September 2005). "General Catalysts for the Suzuki–Miyaura and Sonogashira Coupling Reactions of Aryl Chlorides and for the Coupling of Challenging Substrate Combinations in Water". Angewandte Chemie International Edition. 44 (38): 6173–6177. doi:10.1002/anie.200502017. ISSN   1521-3773. PMID   16097019.
  40. ↑ Carret, Sébastien; Deprés, Jean-Pierre (10 September 2007). "Access to Guaianolides: Highly Efficient Stereocontrolled Total Synthesis of (±)-Geigerin". Angewandte Chemie International Edition. 46 (36): 6870–6873. doi:10.1002/anie.200702031. ISSN   1521-3773. PMID   17676568.
  41. ↑ Milne, Jacqueline E.; Buchwald, Stephen L. (1 October 2004). "An Extremely Active Catalyst for the Negishi Cross-Coupling Reaction". Journal of the American Chemical Society. 126 (40): 13028–13032. doi:10.1021/ja0474493. ISSN   0002-7863. PMID   15469301.
  42. ↑ Cho, Eun Jin; Senecal, Todd D.; Kinzel, Tom; Zhang, Yong; Watson, Donald A.; Buchwald, Stephen L. (25 June 2010). "The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides". Science. 328 (5986): 1679–1681. Bibcode:2010Sci...328.1679C. doi:10.1126/science.1190524. ISSN   0036-8075. PMC   3005208 . PMID   20576888.
  43. ↑ Charles, Mark D.; Schultz, Phillip; Buchwald, Stephen L. (1 September 2005). "Efficient Pd-Catalyzed Amination of Heteroaryl Halides". Organic Letters. 7 (18): 3965–3968. doi:10.1021/ol0514754. ISSN   1523-7060. PMID   16119943.
  44. ↑ Fors, Brett P.; Watson, Donald A.; Biscoe, Mark R.; Buchwald, Stephen L. (15 October 2008). "A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines Using Aryl Chlorides". Journal of the American Chemical Society. 130 (41): 13552–13554. doi:10.1021/ja8055358. ISSN   0002-7863. PMC   2748321 . PMID   18798626.
  45. ↑ Cho, Eun Jin; Senecal, Todd D.; Kinzel, Tom; Zhang, Yong; Watson, Donald A.; Buchwald, Stephen L. (25 June 2010). "The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides". Science. 328 (5986): 1679–1681. Bibcode:2010Sci...328.1679C. doi:10.1126/science.1190524. ISSN   0036-8075. PMC   3005208 . PMID   20576888.
  46. ↑ Teverovskiy, Georgiy; Surry, David S.; Buchwald, Stephen L. (1 August 2011). "Pd-Catalyzed Synthesis of Ar-SCF3 Compounds under Mild Conditions". Angewandte Chemie International Edition. 50 (32): 7312–7314. doi:10.1002/anie.201102543. ISSN   1521-3773. PMC   3395331 . PMID   21692157.
  47. ↑ Bhayana, Brijesh; Fors, Brett P.; Buchwald, Stephen L. (3 September 2009). "A Versatile Catalyst System for Suzuki−Miyaura Cross-Coupling Reactions of C(sp2)-Tosylates and Mesylates". Organic Letters. 11 (17): 3954–3957. doi:10.1021/ol9015892. ISSN   1523-7060. PMC   2759755 . PMID   19663467.
  48. ↑ Watson, Donald A.; Su, Mingjuan; Teverovskiy, Georgiy; Zhang, Yong; García-Fortanet, Jorge; Kinzel, Tom; Buchwald, Stephen L. (25 September 2009). "Formation of ArF from LPdAr(F): Catalytic Conversion of Aryl Triflates to Aryl Fluorides". Science. 325 (5948): 1661–1664. Bibcode:2009Sci...325.1661W. doi:10.1126/science.1178239. ISSN   0036-8075. PMC   3038120 . PMID   19679769.
  49. ↑ Fors, Brett P.; Buchwald, Stephen L. (16 September 2009). "Pd-Catalyzed Conversion of Aryl Chlorides, Triflates, and Nonaflates to Nitroaromatics". Journal of the American Chemical Society. 131 (36): 12898–12899. doi:10.1021/ja905768k. ISSN   0002-7863. PMC   2773681 . PMID   19737014.
  50. ↑ Su, Mingjuan; Buchwald, Stephen L. (7 May 2012). "A Bulky Biaryl Phosphine Ligand Allows for Palladium-Catalyzed Amidation of Five-Membered Heterocycles as Electrophiles". Angewandte Chemie International Edition. 51 (19): 4710–4713. doi:10.1002/anie.201201244. ISSN   1521-3773. PMC   3407381 . PMID   22473747.
  51. ↑ Kirsch, Janelle K.; Manske, Jenna L.; Wolfe, John P. (2018-11-02). "Pd-Catalyzed Alkene Carboheteroarylation Reactions for the Synthesis of 3-Cyclopentylindole Derivatives". The Journal of Organic Chemistry. 83 (21): 13568–13573. doi:10.1021/acs.joc.8b02165. ISSN   0022-3263. PMC   6375689 . PMID   30351050.
  52. ↑ Hutt, Johnathon T.; Wolfe, John P. (2016-09-20). "Synthesis of 2,3-dihydrobenzofurans via the palladium catalyzed carboalkoxylation of 2-allylphenols". Organic Chemistry Frontiers. 3 (10): 1314–1318. doi:10.1039/C6QO00215C. ISSN   2052-4129. PMC   5382964 . PMID   28392926.
  53. ↑ Babij, Nicholas R.; McKenna, Grace M.; Fornwald, Ryan M.; Wolfe, John P. (2014-06-20). "Stereocontrolled Synthesis of Bicyclic Sulfamides via Pd-Catalyzed Alkene Carboamination Reactions. Control of 1,3-Asymmetric Induction by Manipulating Mechanistic Pathways". Organic Letters. 16 (12): 3412–3415. doi:10.1021/ol5015976. ISSN   1523-7060. PMC   4076003 . PMID   24916343.
  54. ↑ Han, Chong; Buchwald, Stephen L. (10 June 2009). "Negishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and Chlorides". Journal of the American Chemical Society. 131 (22): 7532–7533. doi:10.1021/ja902046m. ISSN   0002-7863. PMC   2746668 . PMID   19441851.
  55. ↑ Yang, Yang; Niedermann, Katrin; Han, Chong; Buchwald, Stephen L. (2014-09-05). "Highly Selective Palladium-Catalyzed Cross-Coupling of Secondary Alkylzinc Reagents with Heteroaryl Halides". Organic Letters. 16 (17): 4638–4641. doi:10.1021/ol502230p. ISSN   1523-7060. PMC   4156254 . PMID   25153332.
  56. ↑ Zhang, Hu; Buchwald, Stephen L. (2017-08-23). "Palladium-Catalyzed Negishi Coupling of α-CF 3 Oxiranyl Zincate: Access to Chiral CF3 -Substituted Benzylic Tertiary Alcohols". Journal of the American Chemical Society. 139 (33): 11590–11594. doi:10.1021/jacs.7b06630. ISSN   0002-7863. PMID   28753004.
  57. ↑ "AlPhos and [(AlPhosPd)2•COD] for Pd-Catalyzed Fluorination". Sigma-Aldrich. Retrieved 2018-08-17.
  58. ↑ Sather, Aaron C.; Lee, Hong Geun; De La Rosa, Valentina Y.; Yang, Yang; Müller, Peter; Buchwald, Stephen L. (2015-10-21). "A Fluorinated Ligand Enables Room-Temperature and Regioselective Pd-Catalyzed Fluorination of Aryl Triflates and Bromides". Journal of the American Chemical Society. 137 (41): 13433–13438. doi:10.1021/jacs.5b09308. ISSN   0002-7863. PMC   4721526 . PMID   26413908.
  59. ↑ Sather, Aaron C.; Lee, Hong Geun; De La Rosa, Valentina Y.; Yang, Yang; Müller, Peter; Buchwald, Stephen L. (21 October 2015). "A Fluorinated Ligand Enables Room-Temperature and Regioselective Pd-Catalyzed Fluorination of Aryl Triflates and Bromides". Journal of the American Chemical Society. 137 (41): 13433–13438. doi:10.1021/jacs.5b09308. ISSN   0002-7863. PMC   4721526 . PMID   26413908.
  60. ↑ Shaughnessy, Kevin H. (March 2020). "Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species". Israel Journal of Chemistry. 60 (3–4): 180–194. doi: 10.1002/ijch.201900067 . ISSN   0021-2148. S2CID   202882630.
  61. ↑ Johansson Seechurn, Carin C. C.; Kitching, Matthew O.; Colacot, Thomas J.; Snieckus, Victor (2012-05-21). "Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize". Angewandte Chemie International Edition. 51 (21): 5062–5085. doi:10.1002/anie.201107017. PMID   22573393.
  62. ↑ Ingoglia, Bryan T.; Buchwald, Stephen L. (2017-06-02). "Oxidative Addition Complexes as Precatalysts for Cross-Coupling Reactions Requiring Extremely Bulky Biarylphosphine Ligands". Organic Letters. 19 (11): 2853–2856. doi:10.1021/acs.orglett.7b01082. ISSN   1523-7060. PMC   5580394 . PMID   28498667.
  63. ↑ Uehling, Mycah R.; King, Ryan P.; Krska, Shane W.; Cernak, Tim; Buchwald, Stephen L. (2019-01-25). "Pharmaceutical diversification via palladium oxidative addition complexes". Science. 363 (6425): 405–408. doi: 10.1126/science.aac6153 . ISSN   0036-8075. PMID   30679373. S2CID   59248487.
  64. ↑ Vinogradova, Ekaterina V.; Zhang, Chi; Spokoyny, Alexander M.; Pentelute, Bradley L.; Buchwald, Stephen L. (October 2015). "Organometallic palladium reagents for cysteine bioconjugation". Nature. 526 (7575): 687–691. doi:10.1038/nature15739. ISSN   0028-0836. PMC   4809359 . PMID   26511579.
  65. ↑ Rojas, Anthony J.; Pentelute, Bradley L.; Buchwald, Stephen L. (2017-08-18). "Water-Soluble Palladium Reagents for Cysteine S -Arylation under Ambient Aqueous Conditions". Organic Letters. 19 (16): 4263–4266. doi:10.1021/acs.orglett.7b01911. ISSN   1523-7060. PMC   5818991 . PMID   28777001.
  66. ↑ Jbara, Muhammad; Rodriguez, Jacob; Dhanjee, Heemal H.; Loas, Andrei; Buchwald, Stephen L.; Pentelute, Bradley L. (2021-05-17). "Oligonucleotide Bioconjugation with Bifunctional Palladium Reagents". Angewandte Chemie International Edition. 60 (21): 12109–12115. doi:10.1002/anie.202103180. ISSN   1433-7851. PMC   8143041 . PMID   33730425.
  67. ↑ Lee, Hong Geun; Lautrette, Guillaume; Pentelute, Bradley L.; Buchwald, Stephen L. (2017-03-13). "Palladium-Mediated Arylation of Lysine in Unprotected Peptides". Angewandte Chemie International Edition. 56 (12): 3177–3181. doi:10.1002/anie.201611202. hdl:1721.1/115190. PMC   5741856 . PMID   28206688.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.