Asymmetric Palladium Catalyzed Cross-Coupling Reactions. Topic Talk September 4 th, 2014 Morken Lab Emma Edelstein 1
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1 Asymmetric Palladium Catalyzed Cross-Coupling Reactions Topic Talk September 4 th, 2014 Morken Lab Emma Edelstein 1
2 Palladium Catalyzed Cross-Coupling Reactions 2
3 Kumada/Negishi Cross-Coupling Kumada: Coupling of Grignard reagents Independently reported by Kumada and Corriu in 1972 with Nickel-phosphine complexes Negishi: Coupling of organozinc reagents Reported by Negishi in 1972 to improve functional group tolerance of the Kumada Corriu, J. Chem. Soc., Chem. Commun. 1972, Kumada, J. Am. Chem. Soc. 1972, 94, 9268 Negishi, J. Am. Chem. Soc. 1976, 98, 6729
4 Kumada/Negishi Catalytic Cycle 4
5 First Asymmetric Report L* = Kumada, J. Am. Chem. Soc., 1982, 104, 180; J. Org. Chem. 1983, 48,
6 Investigation of Phosphine Ligands Planar chirality of the ferrocene is important Chelation of the dimethylamino group required for high stereoselectivity Kumada, J. Am. Chem. Soc., 1982, 104, 180 6
7 Resolution Occurring Kumada, J. Am. Chem. Soc., 1982, 104, 180 7
8 Model for Stereo-Induction Stereoselectivity determined during transmetalation Oxidative addition and reductive elimination are stereoretentive Kumada, J. Am. Chem. Soc., 1982, 104, 180 8
9 N-Ar Axially Chiral Mimetic-Type Ligands Aoyama, Tetrahedron, 2004, 60,
10 Asymmetric Negishi Couplings Kumada, Bull. Chem. Soc. Jpn. 1983, 53, 363 Ito, J. Chem. Soc., Chem. Commun. 1989, Pelaz, Tetrahedron: Asymmetry, 2006, 17, 2593
11 Enantioposition Selective Coupling Hayashi, J. Am. Chem. Soc., 1995, 117,
12 Kinetic Resolution Occurring Hayashi, J. Am. Chem. Soc. 1995, 117,
13 Stille Cross-Coupling First report of the coupling of organostannanes published by Eaborn in 1976 Expanded by Kosugi and Migata Stille expanded the scope of the reaction and improved upon previous work in the 1980s Tolerate a wide variety of functional groups Easy to prepare, isolate, and store the organostannane starting materials Major disadvantage: Tin is toxic and it is difficult to remove traces of it Eaborn, J. Organomet. Chem., 1976, 117, C55-C57 Kosugi, Migata, Chem Lett., 1977, ; Stille, J. Am. Chem. Soc,. 1978, 100,
14 Stille Catalytic-Cycle 14
15 Hoppe (2006) Hoppe, Angew. Chem. Int. Ed., 2004, 43, 1423 Hoppe, Syn. Lett. 2006, 12,
16 16 Hoppe, Syn. Lett. 2006, 12, 1959
17 17 Hoppe, Syn. Lett. 2006, 12, 1959
18 Falck (2011) + Biscoe (2013) Falck, Org Lett, 2011, 13, 344 Chong, J. Am. Chem. Soc., 2004, 126, Biscoe, Nat. Chem. 2013, 5,
19 Hiyama Cross-Coupling Fluoride required to activate the silicon for transmetalation Developed to deal with issues associated with organometallic reagents (Zn, Mg, Li, Sn) Hiyama-Denmark Cross-Coupling Doesn t require a fluoride activator Uses silanolate salts Hiyama, J. Org. Chem., 1988, 53, 918 Denmark, Acc. Chem. Res. 2008, 41,
20 Hiyama Catalytic Cycle 20
21 First Asymmetric Report Substrate Controlled Stereochemistry of the product is temperature and solvent dependent Low temperatures: Retention High temperatures: Inversion Polar Solvent: Inversion predominates Non-Polar Solvent: Retention predominates Hiyama, J. Am. Chem. Soc., 1990, 112,
22 Temperature and Solvent Dependence With 3a Solvent Config. ee HMPA:THF 1:10 (R) 8% DMF:THF 1:10 (S) 16% DMSO: THF 1:10 (S) 16% (R) = inversion (S) = retention 3a: 3b: Hiyama, J. Am. Chem. Soc., 1990, 112,
23 Proposed Transition States for Transmetalation Cyclic four-centered transition state promoted by fluoride bridge Present at low temperatures and in low-polarity solvents Unlikely to occur Fluoride bridge is broken inducing a backside attack of Pd Present at high temperatures or in high-polarity solvents Hiyama, J. Am. Chem. Soc., 1990, 112,
24 Expansion to Allyl-Substrates With TASF in THF or with CsF or KF in DMF (S) With CsF, KF in THF (R) 24 Hiyama, Tet. Lett., 1994, 35, 1279
25 Hiyama-Denmark Catalytic Cycle 25
26 Denmark Denmark, J. Am. Chem. Soc. 2008, 130, Denmark, J. Am. Chem. Soc. 2010, 132, 3612
27 27
28 Syn-S E Transmetalation 28 Denmark, J. Am. Chem. Soc. 2010, 132, 3612
29 Alternative Transition State Structure 29 Denmark, J. Am. Chem. Soc. 2010, 132, 3612
30 30
31 Allyl Cross-Coupling (Morken) J. Am. Chem. Soc. 2010, 132, J. Am. Chem. Soc. 2011, 133, 9716 J. Am. Chem. Soc. 2011, 133, Org Lett, 2013, 15,
32 Allyl Cross-Coupling (Morken) J. Am. Chem. Soc. 2014, 136, 7092 J. Am. Chem. Soc., 2012, 134, 8770 Adv. Synth. Catal., 2013, 355, Org. Lett., ASAP. DOI: /ol
33 Suzuki Cross-Coupling First reported by Suzuki and Miyaura in 1979 Mild reaction conditions Much less toxic than organostannanes Many boronic acids are commercially available Tolerate a wide variety of functional groups Can handle aqueous environments 33 Suzuki, Miyaura, J. Chem. Soc., Chem. Commun. 1979, 866; Tetrahedron Lett. 1979, 3437; Synth. Commun. 1979, 11, 513
34 Suzuki Catalytic Cycle 34
35 First Asymmetric Reports Cammidge For ligand screening, X = I, R = H. R = H Cammidge, Chem. Commun. 2000,
36 First Asymmetric Reports - Buchwald Buchwald, J. Am. Chem. Soc. 2000, 122, ; J. Am. Chem. Soc. 2010, 132,
37 Férnandez and Lassaletta Férnandez, Lassaletta, J. Am. Chem. Soc., 2008, 130,
38 38
39 Other Asymmetric Reports Fujihara, Angew. Chem. Int. Ed. 2008, 6917 Yamada, Angew. Chem. Int. Ed. 2009, 48,
40 Other Asymmetric Reports Lin, Org. Lett., 2010, 12, 5546 Senanayake, Org. Lett., 2012, 14,
41 Crudden (2009) 41 Crudden, J. Am. Chem. Soc. 2009, 131, 5024
42 Crudden + Aggarwal (2013) Compound γ:α E/Z Yield e.r. e.s. 83:17 94: : :6 78: : :10 99: : :8 99: :4 100 R γ:α E/Z Yield e.s. H 90:10 99: Me 91:9 99: OMe 85:15 99: COCH 3 90:10 99: Br 90:10 99: CF 3 91:9 99: :2 99: : Aggarwal, Crudden, Chem. Eur. J. 2013, 19, 17698
43 Crudden + Aggarwal (2013) 43
44 Crudden + Aggarwal (2013) 44
45 Ohmura and Suginome (2010) 45 Ohmura, Suginome, J. Am. Chem. Soc. 2010, 132, 13191
46 Proposed Mechanism 46 Ohmura, Suginome, J. Am. Chem. Soc. 2010, 132, 13191
47 Ohmura and Suginome (2011) 47 Ohmura, Suginome, J. Am. Chem. Soc. 2011, 133, 20738
48 Updated Mechanism 48 Ohmura, Suginome, J. Am. Chem. Soc. 2011, 133, 20738
49 Molander (2010) Molander, J. Am. Chem. Soc. 2010, 132,
50 Molander (2012) Molander, J. Am. Chem. Soc. 2012, 134,
51 Hall (2011) 51 Hall, Nat. Chem. 2013, 3, 894
52 Yun (2011) 52 Yun, Angew. Chem. Int. Ed., 2013, 52, 3989
53 Morken (2014) J. Am. Chem. Soc. 2014, 136, 6534 With Bowman Potter and Adam Szymaniak 53
54 Summary Advances in asymmetric variations of the Kumada, Negishi, Stille, Hiyama and Suzuki cross-coupling have been made in the past 30 years Asymmetric cross-coupling proves to be a powerful way to create new C-C bonds and set stereocenters Challenges still present with sp 3 -sp 3 couplings due to β-h elimination and preventing unwanted side-products Not many examples with achiral starting materials Still information to learn about the detailed mechanism of these reactions 54
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