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The Suzuki Reaction Chem 115 Reviews: Analysis of Elementary Steps in the Reaction Mechanism Suzuki, A

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The Suzuki Reaction Chem 115 Reviews: Analysis of Elementary Steps in the Reaction Mechanism Suzuki, A Myers The Suzuki Reaction Chem 115 Reviews: Analysis of Elementary Steps in the Reaction Mechanism Suzuki, A. J. Organometallic Chem. 1999, 576, 147–168. Oxidative Addition Br L Suzuki, A. In Metal-catalyzed Cross-coupling Reactions, Diederich, F., and Stang, P. J., Eds.; Wiley- Br 0 Pd Ln isomerization VCH: New York, 1998, pp. 49-97. Pd L PdII Br L L Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483. cis trans B-Alkyl Suzuki reaction: • Relative reactivity of leaving groups: I – > OTf – > Br – >> Cl –. Chemler, S. R.; Trauner, D.; Danishefsky, S. J. Angew. Chem., Int. Ed. Engl. 2001, 40, 4544–4568. • Oxidative addition is known to proceed with retention of stereochemistry with vinyl halides and with Solid phase: inversion with allylic or benzylic halides. Franzén, R. Can. J. Chem. 2000, 78, 957–962. Stille, J. K.; Lau, K. S. Y. Acc. Chem. Res. 1977, 10, 434–442. • The Suzuki reaction is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide • Oxidative addition intially gives a cis complex that rapidly isomerizes to its trans isomer. or triflate using a palladium catalyst. It is a powerful cross-coupling method that allows for the synthesis of conjugated olefins, styrenes, and biphenyls: Casado, A. L.; Espinet, P. Organometallics 1998, 17, 954–959. Transmetallation n-Bu benzene/NaOEt n-Bu O B + Br – O 80 ˚C, 4 h Path A B(OR)3 X B(OR)2 + L2Pd Ar H OR 98% n-Bu n-Bu B OR n-Bu RO– H + Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866–867. X B(OR) PhL2Pd O L Pd OR 2 R 2 + Mechanism: Ph L2Pd Path B Ph n-Bu n-Bu Ph Br 0 Pd Ln Oxidative Addition L n-Bu O Reductive Elimination II Pd + EtO B L O Ph PdIIL Ph n-Bu n PdIIL Br n • Organoboron compounds are highly covalent in character, and do not undergo transmetallation EtO O B NaOEt readily in the absence of base. O Ph PdIIL • The base is postulated to serve one of two possible roles: reaction with the organoboron reagent to EtO n NaBr form a trialkoxyboronate which then attacks the palladium halide complex (Path A), or by n-Bu conversion of the palladium halide to a palladium oxo complex that reacts with the neutral B O Transmetallation organoboron reagent (Path B). O Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461–470. Carrow, B.P.; Hartwig, J. F. J. Am. Chem. Soc. 2011, 133, 2116–2119. Suzuki, A. Pure & Appl. Chem. 1985, 57, 1749–1758. Andrew Haidle, Chris Coletta, Eric Hansen 1 Reductive Elimination • The conditions shown on the left are the original conditions developed for the cross-coupling by Suzuki and Miyaura. L • The reaction is stereo- and regiospecific, providing a convenient method for the synthesis of n-Bu n-Bu II n-Bu conjugated alkadienes, arylated alkenes, and biaryls. Pd II L Pd + Pd0L L n • Note that under the conditions shown above, aryl chlorides are not acceptable substrates for the L reaction, likely due to their reluctance to participate in oxidative addition. trans cis a Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437–3440. • Isomerization to the cis complex is required before reductive elimination can occur. b Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866–867. • Relative rates of reductive elimination from palladium(II) complexes: c Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11, 513–519. aryl–aryl > alkyl–aryl > n-propyl–n-propyl > ethyl–ethyl > methyl–methyl d Miyaura, N.; Yano, T.; Suzuki, A. Tetrahedron Lett. 1980, 21, 2865–2868. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483. Catalyst and ligands Conditions • The most commonly used system is Pd(PPh ) , but other palladium sources have been used P(PPh ) 3 4 3 4 including PdII pre-catalysts that are reduced to the active Pd0 in situ: R BY2 + X R' R R' benzene, 80 ºC • Pd2(dba)3 + PPh3 base time (h) yield (%) • Pd(OAc)2 + PPh3 • PdCl2(dppf) (for sp3-sp2 couplings-see section on B-alkyl Suzuki reaction) Ph a Br NaOEt 2 80 n-Bu O B • "Ligand-free" conditions, using Pd(OAc)2, have also been developed. Side reactions often Ph O associated with the use of phosphine ligands (phosphonium salt formation and aryl-aryl exchange NaOEt 2 80a Br between substrate and phosphine) are thus avoided. CH Br 3 Goodson, F. E.; Wallow, T. I.; Novak, B. M. Org. Synth. 1997, 75, 61–68. NaOEt 2 81a CH3 I Ph NaOEt 2 100b CH3 H3C CH3 H3C + NaOEt 2 63b N N N N Br Ph b Cl– NaOEt 4 98 H3C CH3 H3C CH3 CH3 H3C CH3 H3C Cl Ph NaOEt 2 3b 1 2 H3CO NaOEt 4 93b Pd2(dba)3 (1.5 mol%), Br H3C (HO)2B 2 (3 mol%), Cs2CO3 + H3C Cl dioxane, 80 ºC, 1.5 h I Ph 2M NaOH 6 62c B(OH)2 96% c Br Ph 2M Na2CO3 6 88 • The nucleophilic N-heterocyclic carbene 1 is the active ligand, and is formed in situ from 2. Cl Ph NaOEt 6 0c • The use of ligand 1 allows for utilization of aryl chlorides in the Suzuki reaction (see the section on d Br 2M NaOH 2 87 bulky, electron-rich phosphines as ligands for use of aryl chlorides as coupling partners as well). n-Bu B Br Zhang, C.; Huang, J.; Trudell, M. L.; Nolan, S. P. J. Org. Chem. 1999, 64, 3804-3805. 2M NaOH 2 99d Andrew Haidle, Chris Coletta, Fan Liu 2 Organoboranes: A variety of organoboranes may be used to effect the transfer of the organic coupling N-methyliminodiacetic acid (MIDA) Boronates partner to the reactive palladium center via transmetallation. Choice of the appropriate organoborane • This trivalent boron protecting group attenuates transmetallation, and is unreactive under will depend upon the compatibility with the coupling partners and availability (see section on synthesis anhydrous coupling conditions (see example below). of organoboranes). H3C N • Some of the more common organoboranes used in the Suzuki reaction are shown below: p-Tol-B(OH)2 H C O 3 N Pd(OAc)2 B O O O O O o B O K3PO4, THF, 65 C R B(OH)2 R B(OiPr)2 R B O O O PCy2 Br H3C R CH3 O CH3 R B B EtO B O CH3 CH 3 • MIDA boronates are stable to chromatography but are readily cleaved under basic aqueous conditions: • Use of Aryltrifluoroborates as Organoboranes for the Suzuki Reaction H3C N 1M NaOH, THF OH O 10 min Pd(OAc)2, K2CO3 B O B O OH BF3K Br OCH3 OCH3 R O R aq. NaHCO CH3OH, reflux 3 2h, 95% MeOH, 3.5 h Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2007, 129, 6716-6717. • The aryltrifluoroborates are prepared by treatment of the corresponding arylboronic acid with Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2008, 130, 14084-14085. excess KHF2. • Many unstable boronic acids, such as 2-heteroaryl, vinyl and cyclopropyl, form bench-stable MIDA complexes. • According to the authors, aryltrifluoroborates are more robust, more easily purified, and less prone to protodeboronation compared to aryl boronic acids. • "Slow release" of boronic acid allows effective coupling of these substrates. Molander, G. A.; Biolatto, B. J. Org. Chem. 2003, 68, 4302–4314. OtBu H C Solvent: The Suzuki reaction is unique among metal-catalyzed cross-coupling reactions in that it can 3 N Ot-Bu be run in biphasic (organic/aqueous) or aqueous environments in addition to organic solvents. Cl O S B O S O O Pd(OAc)2, SPhos Casalnuovo, A. L.; Calabrese, J. C. J. Am. Chem. Soc. 1990, 112, 4324–4330. K3PO4, dioxane, water 60 oC, 6 h 94% (Yield from the corresponding boronic acid: 37%) Knapp, D. M.; Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2009, 131, 6961-6963. Andrew Haidle, Chris Coletta, Eric Hansen 3 TlOH and TlOEt as Rate-Enhancing Additives for the Suzuki Reaction Bulky, Electron-Rich Phosphines as Ligands for the Suzuki Reaction TBSO OTBS R I R Cy2P R TBSO OTBS OTBS P(Cy)3 OTBS OTBS R' OTBS TBSO + (H C) N TBSO OTBS 3 2 P(t-Bu)3 R R = PCy (1) R = PCy (3) O 2 2 R = OCH3, R' = H "SPhos" (HO)2B OTBS R = P(t-Bu) (2) R = P(t-Bu) (4) OTBS 2 2 R = Oi-Pr, R' = H "RuPhos" OTBS OCH3 OTBS R = R' = i-Pr "XPhos" O OTBS R Cl + (HO)2B OCH3 base temp (°C) time yield relative rate KOH 23 2 h 86 1 R ligand Pd source base solvent temp (°C) time (h) yield (%) TlOH a 23 <<30 s 92 1000 CH3 PPh3 Pd2(dba)3 Cs2CO3 dioxane 80 5 0 Pt-Bu Pd (dba) Cs CO dioxane 80 5 86a CH 3 2 3 2 3 • TlOH greatly accelerates the rate of coupling, which the authors attribute to acceleration of the 3 b 4 Pd(OAc)2 KF THF 23 6 95 hydroxyl–halogen exchange at palladium. a Pt-Bu3 Pd2(dba)3 Cs2CO3 dioxane 80 5 89 CH3O 4 Pd(OAc) KF THF 45 6 93b Uenishi, J.; Beau, J.; Armstrong, R. W.; Kishi, Y. J. Am. Chem. Soc. 1987, 109, 4756–4658. 2 a NH2 Pt-Bu3 Pd2(dba)3 Cs2CO3 dioxane 80 5 92 O • TlOH vs. TlOEt a Pt-Bu3 Pd2(dba)3 Cs2CO3 dioxane 80 5 91 H3C t-BuO2C CO2t-Bu (HO)2B OH t-BuO2C CO2t-Bu (5 equiv) a Littke, A.
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