Buchwald Portfolio - Precatalysts and Ligands - Sigma-Aldrich
Buchwald Portfolio - Precatalysts and Ligands - Sigma-Aldrich
Buchwald Portfolio - Precatalysts and Ligands - Sigma-Aldrich
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<strong>Buchwald</strong> <strong>Portfolio</strong> –<br />
<strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s
<strong>Buchwald</strong> <strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s<br />
Dialkylbiaryl phospine lig<strong>and</strong>s, <strong>and</strong> the precatalysts derived from them, are commonly referred to as <strong>Buchwald</strong> <strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s.<br />
These reagents have developed into a highly valuable class of compounds for palladium catalysis, <strong>and</strong> can now be used for a broad range<br />
of reactions. This brochure is designed to show the common uses <strong>and</strong> advantages of these powerful, <strong>and</strong> now commercially available,<br />
<strong>Buchwald</strong> <strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s.<br />
<strong>Buchwald</strong> <strong>Precatalysts</strong><br />
Different Pd Sources <strong>and</strong> Different Methods of Activation in C-N Cross Coupling Reactions<br />
<strong>Buchwald</strong> <strong>Precatalysts</strong> are highly active for a range of Pd-catalyzed reactions. These bench-stable complexes can be activated under mildly<br />
basic conditions <strong>and</strong> provide a number of unique advantages over traditional palladium catalysts in terms of both activity <strong>and</strong> stability.<br />
Pd(OAc) 2<br />
Reduction<br />
Deprotonation<br />
Reductive<br />
elimination<br />
L 1 Pd(0)<br />
Base Active Catalyst<br />
Precatalyst<br />
Reduction not required<br />
<strong>Precatalysts</strong> Pd(OAc) 2 Pd 2 (dba) 3<br />
Air stable Air stable Air stable<br />
• Pd(II) complex<br />
• Efficient formation of active monoligated<br />
catalysts under basic reaction conditions,<br />
without reducing agent<br />
• Low catalyst loading<br />
• Short reaction time<br />
• Pd(II) complex<br />
• Addition of exogenous reductant (NR 3 or<br />
PhB(OH) 2 ) or phosphine lig<strong>and</strong> for reduction<br />
of Pd(II)<br />
• High catalyst loading<br />
• Long reaction time<br />
• Pd(0) complex<br />
• Without reducing agent<br />
• dba can bind Pd center <strong>and</strong> reduce catalytic<br />
activity<br />
• High catalyst loading<br />
• Long reaction time<br />
For bulk quantity inquiries contact: catalysis@sial.com<br />
<strong>Aldrich</strong>.com<br />
Order 800-325-3010 Technical Service 800-325-5832
Structure Cat. No. Common Name CAS No. Mol. Wt. Application for Pd Catalysis<br />
704954 XPhos Precatalyst 1028206-56-5 738.76 • α-Arylation of aldehydes<br />
Pd NH 2<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
Cy 2 P Cl<br />
i Pr<br />
i Pr<br />
i Pr<br />
704954<br />
Pd NH 2<br />
t Bu 2 P Cl<br />
i Pr<br />
708739 tBuXPhos Precatalyst 1142811-12-8 686.69 • α-Arylation of acetate esters<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
i Pr<br />
i Pr<br />
Cy 2 P<br />
708739<br />
Pd NH 2<br />
Cl<br />
OCH 3<br />
t BuOCH 3<br />
704946 SPhos Precatalyst 1028206-58-7 760.72 • <strong>Buchwald</strong>-Hartwig amination<br />
H 3 CO<br />
704946<br />
Pd NH 2<br />
Cy 2 P<br />
Cl<br />
O i Pr<br />
t BuOCH 3<br />
707589 RuPhos Precatalyst 1028206-60-1 816.83 • <strong>Buchwald</strong>-Hartwig amination<br />
i PrO<br />
707589<br />
718750 BrettPhos Precatalyst 1148148-01-9 798.81 • <strong>Buchwald</strong>-Hartwig amination<br />
Cy 2 P<br />
H 3 CO<br />
Pd NH 2<br />
Cl<br />
i Pr<br />
i Pr<br />
CH i Pr 3 O<br />
718750
<strong>Buchwald</strong> <strong>Portfolio</strong> – <strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s<br />
Structure Cat. No. Common Name CAS No. Mol. Wt. Application for Pd Catalysis<br />
Cy 2 P<br />
Pd NH 2<br />
Cl<br />
i Pr<br />
741825<br />
New<br />
2 nd Generation XPhos<br />
Precatalyst<br />
N/A 785.31 • Suzuki coupling<br />
• Low temperature <strong>Buchwald</strong>-<br />
Hartwig amination<br />
• Heck coupling<br />
i Pr<br />
i Pr<br />
741825<br />
753009<br />
New<br />
2 nd Generation SPhos<br />
Precatalyst<br />
N/A 719.19 • Low temperature <strong>Buchwald</strong>-<br />
Hartwig amination<br />
Cy 2 P<br />
Pd NH 2<br />
Cl<br />
OCH 3<br />
H 3 CO<br />
753009<br />
753246<br />
New<br />
2 nd Generation RuPhos<br />
Precatalyst<br />
N/A 775.25 • Low temperature <strong>Buchwald</strong>-<br />
Hartwig amination<br />
Cy 2 P<br />
Pd NH 2<br />
Cl<br />
O i Pr<br />
i PrO<br />
753246
<strong>Buchwald</strong> Lig<strong>and</strong>s<br />
Structural Features of Dialkylbiaryl Phosphine Lig<strong>and</strong>s<br />
R 2 : Increases catalyst stability by<br />
preventing cyclometalation,<br />
Encourages formation of L 1Pd(0)<br />
R 3 : When not equal to H, usually<br />
only for ease of synthesis<br />
R 3<br />
R 2<br />
R 2<br />
PR 2<br />
R 1<br />
: Prevents oxidation at P by O 2,<br />
Accelerates reductive elimination<br />
R 1 : Substitution promotes<br />
reductive elimination<br />
R: Electron-rich groups accelerate<br />
rate of oxidative addition<br />
Structure Cat. No. Common Name CAS No. Mol. Wt. Application for Pd Catalysis<br />
Cy 2 P<br />
PCy 2<br />
638099<br />
PCy 2<br />
H 3 C N<br />
Cy 2 P<br />
638099 Cyclohexyl<br />
JohnPhos<br />
247940-06-3 350.48 • Suzuki coupling<br />
• Negishi coupling<br />
• Hiyama coupling<br />
• Methylation of aryl halides<br />
• α-Arylation of ketones<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
• C-B bond formation<br />
• Oxidation of alcohols to ketones <strong>and</strong> aldehydes<br />
• Kumada-Corriu coupling<br />
• α-Arylation of ketones<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
• Rh-catalyzed hydroamination<br />
CH 3<br />
638021 DavePhos 213697-53-1 393.54 • Suzuki coupling<br />
638021<br />
638064 XPhos 564483-18-7 476.72 • Suzuki coupling<br />
i Pr<br />
• Sonogashira coupling<br />
i Pr<br />
• Hiyama coupling<br />
i Pr<br />
• Stille coupling<br />
• Carbonyl enolate coupling<br />
638064<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
OCH 3<br />
638072 SPhos 657408-07-6 410.53 • Suzuki coupling<br />
• Kumada-Corriu coupling<br />
• Negishi coupling<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
H 3 CO<br />
638072 PCy 2<br />
H 3 C<br />
Cy 2 P695262<br />
i PrO<br />
Cy 2 P663131<br />
H 3 CO i Pr<br />
695262 MePhos 251320-86-2 364.50 • Suzuki coupling<br />
• α-Arylation of ketones<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
O i Pr<br />
663131 RuPhos 787618-22-8 466.64 • Suzuki coupling<br />
i Pr<br />
• Negishi coupling<br />
• α-Arylation reaction of oxindoles<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
718742 BrettPhos 1070663-78-3 536.77 • <strong>Buchwald</strong>-Hartwig amination<br />
• Trifluoromethylation of aryl chlorides<br />
i Pr<br />
CH 3 O<br />
718742<br />
Cy 2 P<br />
OCH 3<br />
O<br />
S ONa<br />
O<br />
H 3 CO<br />
xH 2 O<br />
677280 S<br />
SPhos 1049726-96-6 512.57 • Suzuki coupling<br />
• Rh-catalyzed 1,2-addition of arylboronic acids to<br />
aldehydes <strong>and</strong> ketones<br />
677280
<strong>Buchwald</strong> <strong>Portfolio</strong> – <strong>Precatalysts</strong> <strong>and</strong> Lig<strong>and</strong>s<br />
Structure Cat. No. Common Name CAS No. Mol. Wt. Application for Pd Catalysis<br />
PPh 2<br />
695882 PhDavePhos 240417-00-9 381.45 • α-Arylation of α-amino acid esters<br />
• Heteroarene benzylation<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
H 3 C<br />
H 3 C<br />
N<br />
CH 3<br />
t Bu 2 P i 695882<br />
Pr<br />
i Pr<br />
638080<br />
P t Bu 2<br />
638439<br />
t Bu 2 P<br />
H 3 C i Pr<br />
H 3 C<br />
i Pr<br />
CH 3<br />
675938 P t Bu 2<br />
H 3 C<br />
t 695211<br />
H 3 CO Bu 2 P<br />
CH 3 O i Pr<br />
730998<br />
P t Bu 2<br />
H 3 C N<br />
CF 3 695874<br />
i Pr<br />
i Pr<br />
i Pr<br />
638080 tBuXPhos 564483-19-8 424.64 • α-Arylation of tetramic acids<br />
• Decarboxylative coupling of aromatic acids <strong>and</strong><br />
aryl iodides<br />
• Carboxylation of aryl bromides with CO 2<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
• <strong>Buchwald</strong>-Hartwig C-O coupling<br />
638439 JohnPhos 224311-51-7 298.40 • Suzuki coupling<br />
• Heck coupling<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
• <strong>Buchwald</strong>-Hartwig C-O coupling<br />
• C-Si bond formation<br />
675938 Tetramethyl<br />
di-tBuXPhos<br />
857356-94-6 480.75 • Conversion of aryl halides to phenols<br />
• <strong>Buchwald</strong>-Hartwig amination<br />
• <strong>Buchwald</strong>-Hartwig C-O coupling<br />
695211 tBuMePhos 255837-19-5 312.43 • α-Arylation of ketones<br />
• <strong>Buchwald</strong>-Hartwig C-O coupling<br />
• Formate reduction of N-heterocyclic allylic<br />
acetates<br />
i Pr 730998 tBuBrettPhos 1160861-53-9 484.69 • <strong>Buchwald</strong>-Hartwig amination<br />
• C-F bond formation<br />
• O-Arylation of ethyl acetohydroximate<br />
• Conversion of aryl <strong>and</strong> vinyl triflates to bromides<br />
<strong>and</strong> chlorides<br />
• Conversion of aryl chlorides, triflates, <strong>and</strong><br />
nonaflates to nitroaromatics<br />
• <strong>Buchwald</strong>-Hartwig C-O coupling<br />
• Coupling of ammonia with aryl halides<br />
• C-Si bond formation<br />
CH 3<br />
695874 tBuDavePhos 224311-49-3 341.47 • α-Arylation of esters<br />
731013 JackiePhos 1160861-60-8 796.66 • N-arylation of secondary amides<br />
CF 3<br />
CF 3<br />
F 3 C<br />
CH 3 O<br />
P<br />
i Pr<br />
i Pr<br />
CH 3 O<br />
i Pr<br />
731013<br />
References:<br />
Surry, D. S.; <strong>Buchwald</strong>, S. L. Chem. Sci. 2011, 2, 27-50.<br />
Martin, R.; <strong>Buchwald</strong>, S. L. Acc. Chem. Res. 2008, 41, 1461-1473.<br />
Surry, D. S.; <strong>Buchwald</strong>, S. L. Angew. Chem. Int. Ed. 2008, 47, 6338-6361.<br />
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