Catalytic Conjunctive Cross-Coupling enabled by Metal-Induced Metallate Rearrangement
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1 Catalytic Conjunctive Cross-Coupling enabled by Metal-Induced Metallate earrangement L. Zhang, G. J. Lovinger, E. K. Edelstein, A. A. Szymaniak, M.. Chierchia, J.. Morken Science 2016, 351, Li + d(ac) 2 L1, 2 Tf THF, 60 o C, 14 h then Na, H Mike Wipf Group age 1 of 16 1/16/2016
2 1,2-Metallate Shifts with oron L 2 C' 3 'S ' 2 A = = Cl A = S = Cl L L A = C = Cl A A = N =z A = = NH 2 Mike Wipf Group age 2 of 16 1/16/2016
3 ecent 1,2-Metallate Shifts from oron to Carbon Li 1 2 THF, -78 o C, then NS 1 2 NS r 1,2 shift r Nu Li 1 2 N TrocCl, N N THF, -78 o C 1 2 then H 2 2,Na 1 2 Nature Chem. 2014, 6, J. AM. Chem. Soc. 2015, 137, Mike Wipf Group age 3 of 16 1/16/2016
4 Alkyl-Metal egents Generated from Alkenes L n M L n Alkyl CuCl, (pin) 2, Ligand Litu, DMA, 60 o C I Alkyl or Alkyl Cur, (pin) 2, Ligand Natu,Me, 120 o C oc CuAc, (pin) 2, Ligand, d(dppf)cl 2 K,tuMe, 0 o C (pin) r CuSIMesCl, (pin) 2, d-os precat. Natu,tuMe Angew. Chem. Int. Ed. 2015, 54, J. Am. Chem. Soc. 2015, 137, J. Am. Chem. Soc. 2015, 137, Chem. Eur. J. 2014, 20, Mike Wipf Group age 4 of 16 1/16/2016
5 Stereoinvertive vs. Stereoretentive Transmetallation Tol-r CuSIMesCl, (pin) 2, d-iu 3 precat. NatAmyl, Me Tol-r CuSIMesCl, (pin) 2, d-uos precat. Natu, THF L n Cu r d Tol H 3 r Cy 2 L Cu d H Tol (pin) Angew. Chem. Int. Ed. 2015, 54, Tol Tol Mike Wipf Group age 5 of 16 1/16/2016
6 Suzuki Catalytic Cycle d M M d dl n H L2 d H L2 Mike Wipf Group age 6 of 16 1/16/2016
7 roposed Catalytic Cycle dl n L 2 d d L 2 L 2 d "-hydride or reductive eleimination? L2! acidic enough? Transmetallation Science. 2016, 351, Mike Wipf Group age 7 of 16 1/16/2016
8 -Li Method: eaction Scope 1 Li 1 Li + d(ac) 2 L1, 2 Tf THF, 60 o C, 14 h then Na, H L1 = Fe NMe 2 2 Me 2 NMe 2 83%, 97:3 er ir 66%, 97:3 er hexyl 74%, 98:2 er nu TMS 77%, 97:3 er 48%, 88:12 er Me CF 3 68%, 97:3 er 84%, 97:3 er 51%, 94:6 er 51%, 96:4 er 44%,70:30 er Me Me CH 49%, 98:2 er Me 83%, 98:2 er 68%, 96:4 er Cy 73%, 95:5 er 86%, 97:3 er 73%, 87:13 er hexyl 74%, 94:6 er heptyl 50%, 89:11 er TS C 2 Me 46%, 97:3 er 41%, 90:10 er Science. 2016, 351, Mike Wipf Group age 8 of 16 1/16/2016
9 -Li Method: eaction Scope 1 Li 1 Li + d(ac) 2 L1, 2 Tf THF, 60 o C, 14 h then Na, H L1 = Fe NMe 2 2 NMe 2 Me 2 $99/100 mg 83%, 97:3 er ir 66%, 97:3 er hexyl 74%, 98:2 er nu TMS 77%, 97:3 er 48%, 88:12 er Me CF 3 68%, 97:3 er 84%, 97:3 er 51%, 94:6 er 51%, 96:4 er 44%,70:30 er Me Me CH 49%, 98:2 er Me 83%, 98:2 er 68%, 96:4 er Cy 73%, 95:5 er 86%, 97:3 er 73%, 87:13 er hexyl 74%, 94:6 er heptyl 50%, 89:11 er TS C 2 Me 46%, 97:3 er 41%, 90:10 er Science. 2016, 351, Mike Wipf Group age 9 of 16 1/16/2016
10 Vinyl-Li Method: eaction Scope 1 Li 1 Li + d(ac) 2 L1, Tf THF, 60 o C, 14 h then Na, H L1 = Fe NMe 2 2 Me 2 NMe 2 nu iu Cy 76%, 98:2 er 59%, 99:1 er 84%, 97:3 er 80%, 95:5 er 93%, 99:1 er Me Me Me 77%, 94:6 er Me 83%, 97:3 er F 3 C <5% Cl 66%, 97:3 er 2 N N Me 75%, 95:5 er 86%%, 95:5 er 86%, 95:5 er 67%, 97:3 er 73%, 72:28 er Science. 2016, 351, Mike Wipf Group age 10 of 16 1/16/2016
11 Vinyl-Li Method: Interesting Notes 1 Li 1 Li + d(ac) 2 L1, Tf THF, 60 o C, 14 h then Na, H L1 = Fe NMe 2 2 Me 2 NMe 2 Me Me nu iu Cy 1-2 mol% halide ion detrimental 76%, 98:2 er 59%, 99:1 er 84%, 97:3 er 80%, 95:5 er 93%, 99:1 er Solution: lithium-halogen exchange with n-uli followed by low temperature crystallization of vinyl lithium. Alternatives Me F 3 C Cl Me 77%, 94:6 er 83%, 97:3 er <5% 66%, 97:3 er Increase catalyst loading by 2.5x Li-Sn exchange 2 N N Me 75%, 95:5 er 86%%, 95:5 er 86%, 95:5 er 67%, 97:3 er 73%, 72:28 er Science. 2016, 351, Mike Wipf Group age 11 of 16 1/16/2016
12 reparation of Combretastatin Me 1. TSCl, DIEA, DMF 2. m-ca, CH 2 Cl 2 TS Me C 3. Na 2 C 3, Me 4. yridine, Tf 2, CH 2 Cl 2 81% Tf Me (neo) Me Me + Li 1. d(ac) 2, L1,THF, 60 o C 2. Na, H 2 2, THF 3. TAF, THF 78%, 95:5 er Me Me Me Me Combretastatin Science. 2016, 351, Mike Wipf Group age 12 of 16 1/16/2016
13 D-Labeling Experiment d(ac) 2, L1 D + Li THF, 60 o C, 14 h then Na, H 2 2 D H L n d (pin) H H D (pin) H D H Science. 2016, 351, Mike Wipf Group age 13 of 16 1/16/2016
14 Interesting Future Directions d L 2 2 d 3 L2 L 2 dl n L 2 d L 2 Mike Wipf Group age 14 of 16 1/16/2016
15 Interesting Future Direction d L 2 2 d 3 L2 L 2 dl n L 2 d L 2 Mike Wipf Group age 15 of 16 1/16/2016
16 Sensitivity to couterions Laborious reaction setup Current Drawbacks 1,2-shift of electron deficient aromatics Mike Wipf Group age 16 of 16 1/16/2016
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