SnAP Reagents for the One- Step Synthesis of Medium- Ring Saturated N- Heterocycles from Aldehydes
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1 AP eagets for the e- tep ythesis of Medium- ig aturated - eterocycles from Aldehydes Cam- Va T. Vo, Michael Luescher, ad Jeffrey W. Bode ature Chemistry. doi: /chem.1878 Curret Lit James Johso 1
2 Medium- rig saturated - heterocycles Imiocyclitols Cl Cl PMT ihibitor dovyalici B toocie (+)-Quebrachamie (+)-haziilam aturated - heterocycles as drugs J. Am. Chem. oc. 1996, 118, ; J. Med. Chem. 1996, 39, rg. Le<. 2003, 5, ; J. Am. Chem. oc. 1998, 120, at. Chem. 2012, 4,
3 Li Ar-, M PdL ArMgBr (2 eq) Fe(acac) 3 (5 mol %) t-bume, 50 C mi = i, Br B Ar Ar α- Arylatio of cyclic amies Dieter CuC LiCl Pd(PPh 3 ) 4, (chiral Li) Campos ZCl 2, Pd(Ac) 2, P(t-Bu) 3 - BF 4 (chiral Li) Kochel ZCl 2, Pd 2 dba 3, uphos akamura ArB() 2 u 3 (C) 12 (3.3 mol %) t-bucme (5 eq) 150 C, 4-19 h Ar ames Ar-C, aac Ir(ppy) 3 (1 mol %) DMA 23 C, 12 h Ar MacMilla 3 JAC 2001, 123, ; JAC 2006, 128, ; JAC 2011, 133, ; JAC 2010, 132, ; JAC 2006, 128, ; ciece 2011, 334,
4 = aryl, alkyl = aryl, alkyl 2 2 Previous work M 4Å C 2 Cl 2 2 h, r.t Cu(Tf) 2 2,6-lutidie 4:1 C 2 Cl 2 :PIF 12 h, r.t. M 4Å Cu(Tf) 2 2,6-lutidie Me Me C 2 Cl 2 4:1 C 2 Cl 2 :PIF Me 2 h, r.t 12 h, r.t. 23 examples 40-77% 30 examples 5-94% =, 75% 64% 58% 75% Et 79% dr > 10:1 57% dr > 10:1 Et 63% dr = 5:1 79% <10% 85% 84% Et 79% dr > 10:1 Et 51% dr > 5:1 Et 80% dr > 10:1 4 Vo, C.V.T., MikuUs, G., Bode, J.W., Agew. Chem. It. Ed. 2013, 52, Luescher, M.U., Vo, C.V.T, Bode, J.W., rg. LeZ. 2014, 16,
5 eve- membered rigs 86% =, 2 Ph 75% d.r. = 10:1 M 4Å C 2 Cl 2, 2 h, r.t 55% Cu(Tf) 2 (1 eq) 2,6-lutidie (1 eq) 4:1 C 2 Cl 2 :PIF 12 h, r.t. 66% 86% Et 52% C Ph 74% d.r. = 9:1 Et 41% Et 62% Et 66% Br 78% 43% 71% d.r. = 9:1 Ph 67% d.r. > 10:1 Ph Me 2 C ature Chemistry. doi: /chem % 59% Me 83% 72% 78% 83% 5
6 Eight ad ie- membered rigs =, = 0, 1; m = 1, 3 2 m M 4Å C 2 Cl 2, 2 h, r.t m Cu(Tf) 2 2,6-lutidie 4:1 C 2 Cl 2 :PIF 12 h, r.t. Cl Me 2 C F 46% 38% 20% 45% m Et 34% 52% 39% 79% Et 72% 68% 51% 42% Me Et Br 6 29% 41% 35% 22%
7 Mechaism FIP Cu(II) Cu(I) Cu II =,, 7
8 Mechaistic tudies Cu(Tf) 2 2,6-lutidie 4:1 C 2 Cl 2 :PIF 12 h, r.t. trace CuL TEMP acb 3 Cu(Tf) 2 2,6-lutidie 4:1 C 2 Cl 2 :PIF 12 h, r.t. Ac, Me 8
9 Coclusios AP provides a alterauve method for the sythesis of medium- sized - heterocycles. Uses mild reacuo codiuos. AP reagets air ad moisture stable. toichiometric i Cu ad Future Itermolecular variat 9
10 6-edo C-attack favored by 3.4 kcal/mol 5-exo -attack 6-edo 1:50 5-exo 10
11 Bu 3 ythesis of AP eagets: 1) LDA, TF -78 C - 0 C I. PPh 3 2) (C 2 ), TF TF rt, 4h rt, 12h 73% 93% I 2 K 2 C 3 Et: 2 70 C, 12h 98% 2 Bu 3 1) LDA, TF -78 C - 0 C 2) (C 2 ), TF rt, 4h 3) MsCl, TF -78 C - rt, TF 89% Cl ai acetoe rt, 16h 98% I 11 Agew. Chem. It. Ed. 2013, 52,
12 2 2 2 Et, 0.25 h reflux = 1: quat. = 2: quat a, C 2 I TF/DMF, 15h, 50 C = 1: 94 % = 2: 97 % 2 ythesis of AP eagets 1) MsCl, Et 3, Et 2, 2 h, r.t. 2) K + Phthalimide DMF, 3 h, 100 C = 1: 88 % (2 steps) = 2: 64 % (2 steps) 2 1) LA, TF 3h, 65 C, 92% 2) a, C 2 I DMF, 3h, r.t. 76 % Bu 3 2 1)C 2 I K 2 C 3, Acetoe reflux, 12h Bu Bu 3 2) Phthalimide, DIAD, PPh 3, TF, 16h, r.t. 1) = 1: 69 %; = 3: 89 %. 2) = 1: 66 %; = 3: 95 % Et, 0.3h reflux = 1: 99 % = 3: quat. 2 1) LA, TF 16h, 0 C, 79% 2) a, C 2 I DMF, 16h, r.t. 85 % 3) MsCl, Et 3, Et 2, 2 h, r.t. 4) K + Phthalimide DMF, 3 h, 100 C 90 % (2 steps) Bu Et, 0.3h reflux quat. 2 Bu 3 12
13 2 1) 2, TF, 24h 2) TIPCl, im, C 2 Cl 2, 15 h, r.t 90 % (2 steps) 3) a, C 2 I DMF, 1h, 0 C 91 % 4) TBAF, TF, 1 h, r.t. 96% ythesis of AP reagets 1) Phthalimide, DIAD, PPh 3, TF, 24h, r.t. 2) 22 2 Et, 0.3 h, reflux quat. Bu 3 2 1) 2, Et 3 C 2 Cl 2, 18 h, 1) K + Phthalimide DMF, 0.75 h, Cl r.t. 97% C, 81% 3 Cl 2 2) a, C 2 I DMF, 3h, r.t. 76 % 2) Et, 0.3 h, reflux 95% 13
14 AP for ubstituted Piperazies/ Morpholies Br 1) 2, C 2 Cl h, rt, quat. Br 2) K + Phthalimide DMF, 24 h, r.t 91% 3) a, C 2 I DMF, 5h, 0 C 71% 4) 2 2, Et reflux 30 mi 95% 2 2 Bu 3 1) 2, C 2 Cl 2 18h, rt, 89% 2 Bu 3 1) TrCl, Et 3 C 2 Cl 2 16h, r.t. 92% 2) a, C 2 I DMF, 5h, r.t. 98% 3) Ac, C 2 Cl 2, TFE, 4h, r.t. 90% 1) TBAF, TF, 1h 0 C 2 Bu 3 Bu 3 2) TIPCl, Im, C 2 Cl 2 18h, r.t. 87% 3) a, C 2 I DMF, 5h, r.t., 86% TIP 2) Phthalimide, DIAD, PPh 3, TF, 18h, r.t. 80% (2 steps) 3) 2 2, Et reflux 45 mi, 95% 2 1) a, C 2 I TF/DM, 15h, 55 C, 71% 2) MsCl, Et 3, Et 2 1h, r.t. 3) K + Phthalimide DMF, 3 h, 100 C 82% (2 steps) Bu Et, 0.3h reflux quat. 2 Bu 3 14
15 15
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