Organic Electron Donors
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1 rganic Electron onors Yang Li Zakarian esearch Group epartment of Chemistry and Biochemistry University of California, anta Barbara 11/15/ TAF1 TAE TAF2 TTF BPL
2 utlines rganic Electron onors Background rganic reactions with electron transfers Common electron donor reagents and reduction potentials Typical organic electron donors Early development (TTF, TAE) uper electron donors (TAFs, bispyridinylidene) Application in organic synthesis Application in mechanism studies Transition metal free reaction w/ MEA TAF1 TAE TAF2 TTF BPL 2
3 utlines rganic Electron onors Background rganic reactions with electron transfers Common electron donor reagents and reduction potentials Typical organic electron donors Early development (TTF, TAE) uper electron donors (TAFs, bispyridinylidene) Application in organic synthesis Application in mechanism studies Transition metal free reaction w/ MEA TAF1 TAE TAF2 TTF BPL 3
4 Background rganic reactions with electron transfers ingle electron transfer (ET) is an important process in various redoxand radical-type organic reactions. u u Conversion into an electrophile ET X X X olvent eductive termination E E ET Conversion into a nucleophile 4
5 Background rganic reactions with electron transfers ingle electron transfer (ET) is an important process in various redoxand radical-type organic reactions. u u Conversion into an electrophile ET X X X olvent eductive termination E E ET Conversion into a nucleophile 4
6 Background rganic reactions with electron transfers ingle electron transfer (ET) is an important process in various redoxand radical-type organic reactions. u u Conversion into an electrophile ET X X X olvent eductive termination E E ET Conversion into a nucleophile 4
7 Background rganic reactions with electron transfers ingle electron transfer (ET) is an important process in various redoxand radical-type organic reactions. u u Conversion into an electrophile ET X X X olvent eductive termination E E ET Conversion into a nucleophile 4
8 Background rganic reactions with electron transfers u u Conversion into an electrophile ET X X X olvent eductive termination E E ET Conversion into a nucleophile Common electron donors reagents: Active metals: alkali metals, alkali earth metals Low valent metallic reagents: mi2, TiCl3 rganic metallic reagents: odium naphthaline, CpTiIII J. Broggi, et al. Angew. Chem. Int. Ed. 2014, 53, L. Zhang, L. Jiao, Chem. ci. 2018, 9,
9 Background Classic reactions involved electron donors: Birch reduction 3 C C 3 a, 3, 3 C C 3 44 % Acyloin condensations C 2 Birch, A. J. J. Chem. oc. 1944, a, Et 2, 3, C 2-78 C, 15 min 48 % C 2 2 C Lawton,. G. J. Am. Chem. oc. 1971, 93, 1730 Grigard reaction Cl + e Cl -Cl + e MgCl Mg J. Broggi, et al. Angew. Chem. Int. Ed. 2014, 53, L. Zhang, L. Jiao, Chem. ci. 2018, 9,
10 Background rganic electron donors Es: neutral, ground state organic molecules that reduce substrates by single electron transfer. Advantages: tunable reducing ability, mild reaction conditions Common organic electron donors Tetrakis(demethylamine)ethlyene (TAE) Tetrathiafulvalene (TTF) 2 2 ibenzo-tetraazafulvalene ibenzo-taf TAF1 iimidazo-tetraazafulvalene iimidazo-taf TAF2 Bispyridinylidene BPL J. Broggi, et al. Angew. Chem. Int. Ed. 2014, 53,
11 Background eduction potential -e Cl Br I 2 +e Br I CBr E (V) BPL TAF2 TAF1 E = V E = V E 1 = V E 2 = V TAE E 1 = V E 2 = V TTF E =+0.33 V eduction potential reflects ability to donate electrons Which functional group can accept the electron 7
12 utlines rganic Electron onors Background rganic reactions with electron transfers Common electron donor reagents and reduction potentials Typical organic electron donors Early development (TTF, TAE) uper electron donors (TAFs, bispyridinylidene) Application in organic synthesis Application in mechanism studies Transition metal free reaction w/ MEA 8
13 iscovery of rganic electron donors TAE as an electron donor In 1950, discovery of tetrakis(dimethylamino)ethene (TAE) in industry Its ability to reduce electron poor perfluoro substrates Industrial application of TAE reduction 2 2 F 3 C C 2 F CF 3 C 2 F 5 CF 3 CM, 0C to roomtemp CF 3 CF % 3 F CF 3 F F 2 2 F 3 C + e F CF 3 F C 2 F 5 CF 3 - F F 3 C F CF 3 C 2 F 5 CF 3 + e - F CF 3 CF 3 F F F CF 3 CF F F Lafferty,.., Jr. J. Am. Chem. oc. 1950, 72, 3646 TAE oxidized to its radical anion 4 and di-anion 5 Electron rich ethene & heteroatoms as Es 9
14 iscovery of rganic electron donors TTF as organic electronic material In 1970, inspired by powerful electron donating properties of TAE, Fred Wudl applied Tetrathiafulvalene (TTF) to organic electronics. +e hv, -e ρ = Ω cm + Cl ρ = 3.7 ± 1 Ω cm (4n + 2) π electrons TTF as an excellent organic solid semiconductor. - F. Wuld Aromatic stabilization energy F. Wudl, et al. J. Am. Chem. oc. 1972, 94, F. Wudl, et al. Chem. Commun. 1970,
15 iscovery of rganic electron donors 11
16 iscovery of rganic electron donors TTF as organic donor In 1990s, J. A. Murphy used alkene to trap the benzyl radical generated when treating arenediazonium with TTF. adical-polar crossover reaction using TTF BF a, 6b ET acetone 2 +TTF 1 2 7a: 1 =, 2 = (72%) 7b: 1 = 2 = (56%) Application in total synthesis 2 CCF 3 F 3 CC Et acetone aspidospermidine Chem. Commun. 1993,
17 Background eduction potential -e Cl Br I 2 +e Br I CBr E (V) BPL TAF2 TAF1 E = V E = V E 1 = V E 2 = V TAE E 1 = V E 2 = V TTF E =+0.33 V 13
18 rganic electron donors TAE: a moderate electron donor adical cyclization from benzodiazonium with TAE 2 Br 2 2 Br 2 2 MF 74% J. A. Murphy, Beilstein J. rg. Chem. 2009, 19 adical difluoroalkyl addition to electrophiles Ph 2 2 Ph (1 eq.) CF 2 Br C MF, 90 min (5 equiv.) 70% F F 15 M. debielle J. rg. Chem. 1998, 5385 Ph F F (55%) Et F 2 C (60%) M. debielle, tetrahedron lett. 2001,
19 rganic electron donors TAE: a moderate electron donor adical trifluoromethyl addition to electrophiles TAE (2.2 equiv.) CF 3 I (2.2 equiv.) CF 3 Ar Ar MF, -20 C to rt 18 (68%-95%) 19 W.. olbier, rg. Lett, 2001, 4271 TAE (2.2 equiv.) CF 3 I (5 equiv.) CF 3 MF, 0 C to rt quant W.. olbier, rg. Lett, 2004,
20 rganic electron donors TAE: a moderate electron donor ET to aldehyde by light 22 Cl Ph Ph MF, -20 C to rt hv, 82% TAE, hv 4 2 -Ph 2 Cl 4-2 Ph 24 Cl Ar 4 2 -Ph 25-1 Ar Ph 16
21 Background eduction potential -e Cl Br I 2 +e Br I CBr E (V) BPL TAF2 TAF1 E = V E = V E 1 = V E 2 = V TAE E 1 = V E 2 = V TTF E =+0.33 V 17
22 rganic electron donors uper electron donors : TAFs and bispyridinylidene Tetraazafulvalene or C? tetraazafulvalene trongly favor C carbene Earliest TAFs by J.A. Murphy contained methylene bridges 2 2 BPL E = V I KM 26 MF TAF1 E 1 = V E 2 = V TAF2 E = V J. A. Murphy, Angew. Chem. Int. Ed. 2005, 1356 J. A. Murphy, Angew. Chem. Int. Ed. 2007, 5178 J. A. Murphy, rg. Lett. 2008, 1227 Features: eutral organic molecules Low reduction potential: ET to benzyl iodi (TAF2 and BPL) ET and anionic cyclization 18
23 rganic electron donors uper electron donors : ET v.s. ET 2 TAF1 TAF2 BPL 2 I 27 C 2 Et ET uper electron donors AT MF, Δ C 2 Et ET? TAF1 TAF2 BPL C 2 Et C2 Et (77%) (0%) (21%) (51%) (8%) (83%) 32 J. A. Murphy, Angew. Chem. Int. Ed. 2007, 5178 Et 19
24 rganic electron donors uper electron donors : ET v.s. ET 2 TAF1 TAF2 BPL 2 I +e -I TAF1, KM MF, rt Ph, Δ 33 90% 34 AT (not observed) +e +e (not observed) J. A. Murphy, Angew. Chem. Int. Ed. 2005,
25 rganic electron donors uper electron donors : eactions of iimidazol-taf 2 TAF1 TAF2 BPL 2 Br TAF2 (1.5 equiv.) MF, 100 C 99% Ph 2 2 Ph TAF2 (3 equiv.) MF, 110 C Ph 2 96% tbu I Cl tbu TAF2 (1.5 equiv.) MF, 100 C BPL MF 99% tbu tbu TAF2 (6 equiv.) MF, 110 C, 4h 91% tbu 91% tbu J. A. Murphy, Angew. Chem. Int. Ed. 2007, 5178 J. A. Murphy, J. Am. Chem. oc. 2007, 129,
26 rganic electron donors uper electron donors : bispyridinylidene ET to benzenes BPL hv, MF, rt 66% cis:trans 70:30 6% Et nbu BPL (3 equiv.) hv, MF, rt 91% Murphy, Angew. Chem. Int. Ed. 2012, 3673 Et nbu Murphy, Angew. Chem. Int. Ed. 2013, 2239 BPL (6 equiv.) hv, MF, rt 73% Murphy, Angew. Chem. Int. Ed. 2014,
27 ynthetic applications of organic electron donors Electron onor ET edox potential (vs CE) educed bond Promoted reaction TTF TAE 1 e V, V (C 3 C) Ar- 2 + BF 4-1 e V, V (C 3 C) V (MF) Ar- + 2 BF - 4 ArCCl 3 CF 3 I/CF 3 Br C()CBr radical cyclization radical translocation radical cyclization radical addition (C, ) trifluoromethylation 1 e V, V (MF) Ar-I radical cyclization 2 e V (MF) Ar-I ArBr ArCl C 2 Ph Ts anionic cyclization reduction of haloarene reductive cleavage of sulfone and sulfonamide e V (MF) Tf Tf C() anionic cyclization reduction of haloarene reductive cleavage of sulfone and sulfonamide triflate ester, Weinreb amide 23
28 More than organic electron donors Photosynsitizer for Ar-Cl F Cl CeCl 3 (1 eq.) 0.1 M Et 4 Cl in C 3 C Black light CFLs 2, 40 h 69% F via [CeCl 6 ] 3 - electron donor: E = V (Cp 2 Fe) M. Anna and E. J. chelter, J. Am. Chem. oc. 2016, 138, In-situ generated super electron donor Ph + B 2 Pin 2 + K (1 equiv.) (1.1 equiv.) (1.1 equiv.) 18-C-6 (1.1 equiv.) TF, rt, 2 h 77 % yield 18-C-6 Ph K B Ph A B (super electron donor) E = -1.1 V (CE) Ts Ph (20 mol%) B 2 Pin 2 (1.3 eq.) K (1.3 eq.) MTBE, 85 C, 12 h (86%) A (40 mol%) B 2 Pin 2 (1.3 eq.) K (1.3 eq.) B 2 Pin 2 (1.3 eq.) K (1.3 eq.) MTBE, 85 C, 1 h (96%) L. Zhang and L. Jiao, Chem. ci. 2018, 9,
29 Transient electron donor eaction: I + 20 mol% MEA KBu t, 80 C chanism: Lei, A. W. J. Am. Chem. oc. 2012, 132, organic additive MEA base? trong electron donor ET Chain Initiation I I cleavage ET I Chain Propagation addition Ar 1 proton abstraction Base Tuttle, T., Murphy, J. A., J. Am. Chem. oc. 2014, 136,
30 Transient electron donor What is the Electron donor that traggers the reaction? a. Initiation mechanism 1: (as an electron donor?) trong electron donor? b. Initiation mechanism 2: (as a ligand?) c. Initiation mechanism 3: t -BuK t -BuK ET K t Bu trong electron donor? t -BuK Ar 1 -X Ar 1 -X K ET Ar 1 -X Ar 1 -X t Bu Ar 1 -X Ar 1 -X (as a precursor to electron donor) trong electron donor? ET Tuttle, T., Murphy, J. A., J. Am. Chem. oc. 2014, 136, Jiao, L., J. Am. Chem. oc. 2016, 138,
31 Thank you! Yang Li Zakarian esearch Group epartment of Chemistry and Biochemistry University of California, anta Barbara 11/15/ TAF1 TAE TAF2 TTF BPL
32 TAF1 as a one electron donor I TAF1, KM MF, rt Ph, Δ 90% (not observed) +e -I AT +e +e (not observed) Murphy, Angew. Chem. Int Ed. 2005, 1356
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