Functionalization of C O Bonds. Stefan McCarver. MacMillan Lab Group Meeting
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1 Functionalization of C Bonds Stefan McCarver MacMillan Lab Group eting November 23 rd, 2016
2 Functionalization of C Bonds "X" X homolytic cleavage catalyst M oxidative addition
3 Why is C Bond Manipulation Important? Lignin n Second most abundant biopolymer n About 30% of organic carbon on earth n Byproduct of paper production n Potential fine chemical feedstock
4 Why is C Bond Manipulation Important? biomass conversion () n
5 Why is C Bond Manipulation Important? biomass conversion () n startup company (founded 2014) based on one step removal of lignin from biological feedstocks and upgrading to valuable commodity chemicals
6 Why is C Bond Manipulation Important? complex molecule total synthesis S 1) Bu 3 Sn S 2) BBr 3 ( )-colombiasin A most alkyl halides are derived from the corresponding alcohol versatile for cross coupling Br X stable and widely or derivatization available Nicolau, K. C.; Vassilikogiannakis, W.; Mägerlein, W.; Kranich, R. Angew. Chem. Int. Ed. 2001, 40, 2482
7 Activation of C Bonds is Challenging Br > > 112 kcal/mol 101 kcal/mol 84 kcal/mol > > Br 96 kcal/mol 86 kcal/mol 74 kcal/mol carbon oxygen bonds are much stronger than the corresponding carbon halide bonds Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36, 255
8 Functionalization of C Bonds n Radical alcohol deoxygenation n Thiocarbonyl methods n osphite activation X n Thiol catalysis n Titanium-mediated deoxygenation n Transition metal C bond insertion n Aryl methyl ether electrophiles M n Ru directed C bond insertion n enol cross-coupling
9 Reduction of C Bonds X activating group e.g. Barton-McCombie radical deoxygenation direct deoxygenation (few examples) halide/pseudohalide X Br, Tf, Ms Ac, S 3 R dehalogenation errmann, J. F.; König, B. Eur. J. rg. Chem. 2013, 7017
10 Reduction of C Bonds X activating group e.g. Barton-McCombie radical deoxygenation direct deoxygenation (few examples) halide/pseudohalide X Br, Tf, Ms Ac, S 3 R dehalogenation errmann, J. F.; König, B. Eur. J. rg. Chem. 2013, 7017
11 General Functionalization thods are Not Yet Available direct functionalization? R errmann, J. F.; König, B. Eur. J. rg. Chem. 2013, 7017
12 The Barton-McCombie Alcohol Deoxygenation ipr Bu 3 Sn ipr S, reflux X S S SnBu 3 S SnBu 3 N N Bu 3 Sn N N N N conversion from C=S to C= provides thermodynamic driving force Barton, D.. R.; McCombie, S. W. Perkin Trans. I. 1975, 1574
13 Catalytic Barton-McCombie Deoxygenation S 15 mol% Bu 3 Sn PMS, AIBN, reflux 75% yield (catalytic) 79% (stoichiometric) S Bu 3 Sn R 3 Si TMS Si TMS n R R PMS R R Bu 3 Sn R 3 Si Lopez, R. M.; ays, D. S.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 6949
14 Tin-Free C Bond Reductions general deoxygenation scheme derivatization X reduction X deoxygenation reactions driven by P 2 n entropy electrochemical reduction n formation of =X bond n typically irreversible TBS polarity-reversal catalysis
15 Electrochemical Reduction of Diphenylphosphinate Esters graphite electrode 100 ma cm 2 P DMF, 60 ºC P 0.15 M NBu 4 BF V (Ag/AgCl) = 2.1 V (SCE) electrolysis at 2.4 V (Ag/AgCl) only provided trace product Lam, K.; Marko, I. E. rg. Lett. 2011, 13, 406
16 Electrochemical Reduction of Diphenylphosphinate Esters fragmentation rates support a radical mechanism R () 2 P + e k R () 2 P R () 2 P R k ethyl 0.19 cyclohexyl adamantyl 0.70 allyl too fast to measure Lam, K.; Marko, I. E. rg. Lett. 2011, 13, 406
17 Electrochemical Reduction of Diphenylphosphinate Esters graphite electrode 33 ma cm 2 P DMF, 110 ºC P 0.15 M NBu 4 BF 4 solvent yield DMS CN NMP DMF 0% 0% 43% 44% Lam, K.; Marko, I. E. rg. Lett. 2011, 13, 406
18 Electrochemical Reduction of Diphenylphosphinate Esters fragmentation rates support a radical mechanism R () 2 P + e k R () 2 P R () 2 P R k ethyl 0.19 cyclohexyl adamantyl 0.70 allyl too fast to measure Lam, K.; Marko, I. E. rg. Lett. 2011, 13, 406
19 Electrochemical Reduction of Diphenylphosphinate Esters graphite electrode 100 ma cm 2 R () 2 P R DMF, 60 ºC 0.15 M NBu 4 BF 4 P Ac P P 55% 81% 74% TMS Lam, K.; Marko, I. E. rg. Lett. 2011, 13, 406
20 In Situ osphine Activation P 3 C 9 19 C 9 19 electrolysis can the phosphine intermediate be formed in situ? Maeda,.; Maki, T.; Eguchi, K.; Koide, T.; hmori,. Tet. Lett. 1994, 35, 4129
21 In Situ osphine Activation phosphine constant current at 25 ma C 9 19 C 9 19 CN,Et 4 NX phosphine triethylammonium salt total electricity yield P 3 BF 4 5 F/mol trace P 3 Cl 5 F/mol 66% P 3 Br 5 F/mol 94% P 3 Br 4 F/mol 70% PBu 3 Br 5 F/mol 68% none Br 5 F/mol 0% phosphine necessary for reduction to occur Maeda,.; Maki, T.; Eguchi, K.; Koide, T.; hmori,. Tet. Lett. 1994, 35, 4129
22 In Situ osphine Activation P 3 constant current at 25 ma C 9 19 C 9 19 CN,Et 4 N + Br 94% + C 9 19 P oxidation reduction P 3 P 3 C 9 19 C 9 19 anode cathode Maeda,.; Maki, T.; Eguchi, K.; Koide, T.; hmori,. Tet. Lett. 1994, 35, 4129
23 In Situ osphine Activation PR 3 constant current at 25 ma R R CN,Et 4 N + Br Br 96% (P 3 ) 89% (P 3 ) 86% (PBu 3 ) C % (PBu 3 ) 48% (PBu 3 ) 79% (P() 3, 50 ma) Maeda,.; Maki, T.; Eguchi, K.; Koide, T.; hmori,. Tet. Lett. 1994, 35, 4129
24 thods for Tertiary Alcohol Deoxygenation are Rare many radical deoxygenation methods exist activated esters often thermally unstable
25 Polarity Reversal Activation of MM Ethers (tbu) 3 SiS (cat.) initiator (cat.) octane, reflux reaction conditions 88% 87% 90%, 10:1 dr Dang,.-S.; Franchi, P.; Roberts, B. P. Chem. Commun. 2000, 499
26 Polarity Reversal Activation of MM Ethers Et tbu tbu Δ R tbu tbu Si S tbu alkyl radical cannot abstract to continue radical chain thiol polarity reversal catalyst enables efficient turnover tbu tbu Si S tbu AT AT tbu tbu Si S tbu Dang,.-S.; Franchi, P.; Roberts, B. P. Chem. Commun. 2000, 499
27 Polarity Reversal Activation of MM Ethers (tbu) 3 SiS (cat.) initiator (cat.) octane, reflux reaction conditions 88% 87% 90%, 10:1 dr Dang,.-S.; Franchi, P.; Roberts, B. P. Chem. Commun. 2000, 499
28 Polarity Reversal Activation of MM Ethers (tbu) 3 SiS (cat.) initiator (cat.) octane, reflux reaction conditions 1) Swern oxidation 2) methyl Grignard 3) MM-Cl protection 4) deoxygenation formal to methyl Dang,.-S.; Franchi, P.; Roberts, B. P. Chem. Commun. 2000, 499
29 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane Ti III Cl Ti III Cl Cl Ti III reductant lewis acidic significant bond weakening Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
30 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane R Cp 2 TiCl Cl Cp 2 Ti R R Cl Cp 2 Ti R Cp 2 TiCl fast R TiCp 2 Cl + R alcohol coordination to Ti(III) n inner sphere reduction n trapping of radical by Ti(III) Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
31 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane C 14 90% 83% 45% (45% elimination) Bz Bz 92% 70% Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
32 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane TiCp 2 Cl TiCp 2 Cl TiCp 2 Cl() TiCp 2 Cl TiCp 2 Cl() Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
33 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane C 14 90% 83% 45% (45% elimination) Bz Bz 92% 70% Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
34 Titanium diated Alcohol Reduction 2.0 equiv Cp 2 Ti III Cl 1.5 equiv Mn R R TF or toluene aliphatic alcohol reflux alkane Bz Bz Bz Bz Bz Ti Cp 2 Cl Ti Cp 2 Cl R Barrero, A. F. et al rg. Biomol. Chem. 2015, 13, 3462
35 Titanium Catalyzed Alcohol Reduction Ti III Cl Ac Ti III Cl Catalytic Titanium Ti IV Cp 2 TiCl 0.3 eq Reduction Mn Cl TiIV Cl TMS TMS 2 TMSCl Ac 85% (38% stoichiometric) Barrero, A. F. et al J. Am. Chem. Soc. 2010, 132, 254
36 Functionalization of C Bonds n Radical alcohol deoxygenation n Thiocarbonyl methods n osphite activation X n Thiol catalysis n Titanium-mediated deoxygenation n Transition metal C bond insertion n Aryl methyl ether electrophiles M n Ru directed C bond insertion n enol cross-coupling
37 First Report of Aryl thyl Ether Cross-Coupling MgBr NiCl 2 (P 3 ) 2 tbu benzene, reflux tbu 75% as above 77% much more efficient for napthyl ethers, although some reactivity observed for anisoles Wenkert, E.; Michelotti, E. L.; Swindell, C. S. J. Am. Chem. Soc. 1979, 101, 2246
38 Extension to Anisole Electrophiles p-tolmgbr 3 eq NiCl 2 (ligand) 2 5% ipr 2, 60 ºC ligand Ar yield PEt 3 PiBu 3 PiPr 3 PCy 3 P 2 Cy 75% 32% < 1% 0% 7% 7% 42% 82% 93% 81% P 3 74% 15% Dankwardt, J. W. Angew. Chem. Int. Ed. 2004, 43, 2428
39 Extension to Anisole Electrophiles ArMgBr 3 eq NiCl 2 (ligand) 2 5% Ar ipr 2, 60 ºC N 2 N 75% 82% 73% N 58% 51% Dankwardt, J. W. Angew. Chem. Int. Ed. 2004, 43, 2428
40 thyl Ether Kumada Cross-Couplings p-tol NiCl 2 (PCy 3 ) 2 NiCl 2 (PCy 2 ) 2 p-tolmgbr N MgBr N non-extended aromatics heterocycles Angew. Chem. Int. Ed. 2004, 43, 2428 Angew. Chem. Int. Ed. 2004, 43, 2428 NiCl 2 (PCy 3 ) 2 NiCl 2 (dppf) MgBr MgBr alkyl Grignards benzylic ethers Chem. Commun. 2008, 1437 J. Am. Chem. Soc. 2008, 130, 3268
41 Aryl thyl Ether Cross-Couplings MgBr R B R poor functional group compatibility limited availability challenging to prepare air and moisture stability widespread availability potentially lower reactivity development of an aryl methyl ether Suzuki-Miyaura coupling would be highly advantageous
42 Aryl thyl Ether Suzuki-Miyaura [Ni(cod) 2 ] / PCy 3 B, CsF, 120 ºC 93% 55% 14% 0% Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem. Int. Ed. 2008, 47, 4866
43 Aryl thyl Ether Suzuki-Miyaura [Ni(cod) 2 ] / PCy 3 Ar R B, CsF, 120 ºC F C 2 N 2 65% 83% 79% 74% Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem. Int. Ed. 2008, 47, 4866
44 Aryl thyl Ether Suzuki-Miyaura [Ni(cod) 2 ] / PCy 3 B, CsF, 120 ºC requirement for extended conjugation suggests an alternative oxidative addition mechanism X X Ni 0 Ni I XNi II Ni 0 Ni II NiII X Ni I Kochi electron transfer A nucleophilic type A Tobisu, M.; Shimasaki, T.; Chatani, N. Angew. Chem. Int. Ed. 2008, 47, 4866
45 Aryl thyl Ether Suzuki-Miyaura Ar effective electrophile in Kumada but not Suzuki-Miyaura coupling B [Ni(cod) 2 ] / PCy 3, CsF, 120 ºC 0% yield Et MgBr NiCl 2 (PCy 3 ) 2 73% yield (Et) 2 C 2, 90 ºC Dankwardt, J. W. Angew. Chem. Int. Ed. 2004, 43, 2428 Wenkert, E.; Michelotti, E. L.; Swindell, C. S. J. Am. Chem. Soc. 1979, 101, 2246
46 Aryl thyl Ether Suzuki-Miyaura Cy 3 P Cy 3 P Ni 0 Cy 3 P Cy 3 P Ni II oxidative addition unfavorable Cy 3 P Cy 3 P Ni 0 Cy 3 P MgBr 2 Ni Cy 3 P MgBr + Cy 3 P Cy 3 P Ni II "ate" complex enhanced nucleophilicity Wenkert, E.; Michelotti, E. L.; Swindell, C. S. J. Am. Chem. Soc. 1979, 101, 2246
47 Directed Ru C Bond Cross Coupling tbu B R Ru 2 (C)(P 3 ) 3 4% toluene, reflux Ar tbu tbu 3 P tbu 3 P tbu tbu [Ru] C activation ArB(R) 2 Ru C P 3 C Ru Ar P 3 Ar Kakiuchi, F.; Tsui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2004, 126, 2706
48 Directed Ru C Bond Cross Coupling tbu B R Ru 2 (C)(P 3 ) 3 4% toluene, reflux Ar tbu tbu tbu tbu tbu 76% 96% 81% 50% Kakiuchi, F.; Tsui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2004, 126, 2706
49 Directed Ru C Bond Cross Coupling tbu Ru 2 (C)(P 3 ) 3 toluene RT, 14 h Ar tbu Ru C P 3 toluene 80 ºC, 3 h tbu 3 P Ru C Ar P 3 P 3 kinetic product thermodynamic product Uno, S.; Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516
50 Directed Ru C Bond Cross Coupling tbu Ru 2 (C)(P 3 ) 3 toluene RT, 14 h Ar tbu Ru C P 3 toluene 80 ºC, 3 h tbu 3 P Ru C Ar P 3 P 3 first example of an isolated aryl C bond oxidative addition complex with transition metal Uno, S.; Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516
51 Directed Ru C Bond Cross Coupling TMS B Ru 2 (C)(P 3 ) 3 toluene, reflux TMS 2 equiv 2 equiv 93% complete selectivity Uno, S.; Mizushima, E.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2006, 128, 16516
52 Activation of C Bonds is Challenging Br > > 112 kcal/mol 101 kcal/mol 84 kcal/mol > > Br 96 kcal/mol 86 kcal/mol 74 kcal/mol carbon oxygen bonds are much stronger than the corresponding carbon halide bonds Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36, 255
53 enolic C Bond Cross-Coupling reaction conditions M MgX NiF 2, PCy ºC reaction conditions [{2-NapMgBr(TF) 2 } 2 ] Yu, D.-G.; Li, B.-J.; Zheng, S.-F.; Guan, B.-T.; Wang, B.-Q.; Shi, Z.-J. Angew. Chem. Int. Ed. 2010, 49, 4566
54 enolic C Bond Cross-Coupling M MgX NiF 2, PCy ºC metal salt halide GC yield Li + K + Na + Mg +2 Mg +2 Mg +2 Br Br Br Br Cl I 8% 14% 81% 99% 64% 87% Yu, D.-G.; Li, B.-J.; Zheng, S.-F.; Guan, B.-T.; Wang, B.-Q.; Shi, Z.-J. Angew. Chem. Int. Ed. 2010, 49, 4566
55 enolic C Bond Cross-Coupling R Ni(PCy 3 ) n Ar TF Mg Br 2 MgBr L Ni Ar R Nickel Catalytic Cycle L Ar Ni Mg S Br 2 Mg +2 activation of phenol C bond towards oxidative addition R MgX L Ni R Mg Mg X Br 2 S Yu, D.-G.; Li, B.-J.; Zheng, S.-F.; Guan, B.-T.; Wang, B.-Q.; Shi, Z.-J. Angew. Chem. Int. Ed. 2010, 49, 4566
56 enolic C Bond Cross-Coupling M R MgX NiF 2, PCy 3 R R 120 ºC R N TMS 67% 73% 86% TBS N 89% 77% 67% Yu, D.-G.; Li, B.-J.; Zheng, S.-F.; Guan, B.-T.; Wang, B.-Q.; Shi, Z.-J. Angew. Chem. Int. Ed. 2010, 49, 4566
57 Benzylic Alcohol C Bond Cross-Coupling 1.2 equiv MgBr 10 mol% NiCl 2 (PCy 3 ) 2, 20 mol% PCy 3 Ar MgCl Ar nbu 2 : (1:3), 60 ºC, 24 h methyl Grignard reagent to form magnesium alkoxide benzylic alcohol C bond weaker than phenol - reflected in lower T required Yu, D.-G.; Wang, X.; Zhu, R.-Y.; Luo, S.; Zhang, X.-B.; Wang, B.-Q.; Wang, L.; Shi, Z.-J. J. Am. Chem. Soc. 2012, 134, 14638
58 Benzylic Alcohol C Bond Cross-Coupling 1.2 equiv MgBr 10 mol% NiCl 2 (PCy 3 ) 2, 20 mol% PCy 3 Ar MgCl Ar nbu 2 : (1:3), 60 ºC, 24 h N N 48% 61% 50% F 62% 87% 67% alkyl Grignard reagents were not effective Yu, D.-G.; Wang, X.; Zhu, R.-Y.; Luo, S.; Zhang, X.-B.; Wang, B.-Q.; Wang, L.; Shi, Z.-J. J. Am. Chem. Soc. 2012, 134, 14638
59 Benzylic Alcohol C Suzuki-Miyaura Pd(P 3 ) 4 10% Ar Ar B(R) 2 Ar TF B B B B B 42% 20% 67% Cao, Z.-C.; Yu, D.-G.; Zhu, R.-Y.; Wei, J.-B.; Shi, Z.-J. Chem. Commun. 2015, 51, 2683
60 Benzylic Alcohol C Suzuki-Miyaura Pd(P 3 ) 4 10% Ar Ar B(R) 2 Ar TF coordination of alcohol to phenylboroxine occurs Cao, Z.-C.; Yu, D.-G.; Zhu, R.-Y.; Wei, J.-B.; Shi, Z.-J. Chem. Commun. 2015, 51, 2683
61 Benzylic Alcohol C Suzuki-Miyaura Pd(P 3 ) 4 10% Ar Ar B(R) 2 Ar TF BocN Ac 78% 71% 80% 2 N 85% 41% Cao, Z.-C.; Yu, D.-G.; Zhu, R.-Y.; Wei, J.-B.; Shi, Z.-J. Chem. Commun. 2015, 51, 2683
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