Nickel-Catalyzed Reductive Cross-Electrophile-Coupling Between Aryl and Alkyl Halides

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1 ickel-catalyzed Reductive Cross-Electrophile-Coupling Between Aryl and Alkyl Halides Eunjae Shim Zakarian Group Literature Talk / Dec 13 th, 2018 University of California, Santa Barbara

2 Table of Contents Background Development of Cross Coupling of Ar-X + Alkyl-X - Daniel Weix s contribution Mechanistic Studies ther Methodologies utlook

3 Background : Cross Coupling Ar 1 X + Ar 2 [M] TM cat. Ar 1 Ar 2 Reaction Ar 2 [M] Suzuki-Miyaura Ar B(H) 2 Kumada egishi Ar-MgX Ar-ZnX Stille Ar-SnR 3 Hiyama Ar-Si(R) 3 Sonogashira Alkyne-Cu rganometallic nucleophile - Formation requires separate step - Moisture- and air-sensitive - Limited FG compatibility - May require large excess of one halide

4 Background : Cross-Electrophile-Coupling Wurtz Coupling (1855) 2 R X 2 a 2 ax - Homocoupling of Alkyl Halides - Side reactions : alkene formation hydrodehalogenation R R Ullmann Coupling (1901) Cu 0 2 Ar X Ar Ar - Homocoupling of Aryl Halides Challenge - Cross-selectivity - Side reactions - Easy setup - Stoichiometry between coupling partners Cross-coupling without organometallic intermediacy - Commercial availability - Moisture- and air-tolerance - Wide FG compatibility Ar-, Ar-Br <cf> 2954 Ar-B(H) Alkyl-, 9856 Alkyl-Br <cf> 183 Alkyl-B(R) 2 D. J. Weix et al., J. Am. Chem. Soc., 2010, 132,

5 Weix s Pioneering Work i 2 xh 2 (10.7mol%) Ligand 1 (5mol%) Ligand 2 (5mol%) C 8 H 17 + C 8 H mmol 0.5mmol Pyridine (10mol%) Mn 0 (2eq) DMPU, 80ºC 88% Ph 2 P PPh 2 Ligand 1 (dtbbpy) Ligand 2 C 8 H 17 C 8 H 17 C 8 H 17 B 82% H 78% Ac 77% Et HBoc 77% 85% 64% C 5 H 11 - P / Branched isomer / Linear isomer = 89 : 7: 4 - solated : P / Branched isomer = 95 : 5 88% D. J. Weix et al., J. Am. Chem. Soc., 2010, 132,

6 Weix s Pioneering Work i 2 xh 2 (10.7mol%) Ligand 1 (5mol%) Ligand 2 (5mol%) C 8 H 17 + C 8 H mmol 0.5mmol Pyridine (10mol%) Mn 0 (2eq) DMPU, 80ºC 88% Ph 2 P PPh 2 Ligand 1 (dtbbpy) Ligand 2 Lessons from optimization - Pyridine : less ß- hydride elimination - Solvent : amide based solvents work (>60%) Preliminary mechanistic studies : Ruling out R-Mn-X intermediacy 1) literature 2) TDAE instead of Mn : 57% yield 3) Control rxn : Mn 0, Py (10mol%) R DMPU, 80ºC, 24hr R Mn D. J. Weix et al., J. Am. Chem. Soc., 2010, 132,

7 Further Development Br + Br C 8 H 17 i 2 xh 2 (10mol%) Ligand 3 (10mol%) Pyridine (10mol%) a (25mol%) 0.5mmol 0.5mmol Zn 0 (2eq) DMPU, 60ºC 77% C 8 H 17 Me Me Ligand 3 (dmebpy) phen C 2 Et C 2 Et C 2 Et C 2 Bn 83% TBS H 5mol% L3, 1.25eq Alk-Br 76% Me 2 5mol% L3, 72% Et 5mol% phen, 1eq a 80ºC, 60% C Ts 5mol% L3, 68% C 2 Et 5mol% phen, 76% Tf 5mol% L3, 76% E : Z = 9 : 1 C 2 Et 5mol% phen, 74% C 2 Et C 2 Et C 2 Et C 2 Et Ac 5mol% phen, 64% Bpin 5mol% phen, 76% H Si 5mol% L3, 67% Sn 5mol% L3, 74% D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

8 Preliminary Mechanistic Studies 1. Lessons from optimization Br + Br C 8 H 17 i 2 xh 2 (10mol%) Ligand 3 (10mol%) Pyridine (10mol%) a (25mol%) 0.5mmol 0.5mmol Zn 0 (2eq) DMPU, 60ºC 77% C 8 H 17 Role of iodide - Facilitate reduction of i cat. (act as a bridging ligand) - Form reactive nickelates - Form alkyl- in situ - Facilitate ligand exchange Condition Product Benzene ctane ptimized ºC ºC ncreased direct Zn insertion detrimental to yield Halides Time GC Yield Br-Ph + Br-8 77 Br-R only 53 (Dimer) 45 Br-Ph only 53 (Dimer) 24 Homocoupling significantly Slower than cross-coupling D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

9 Preliminary Mechanistic Studies 2. Rate vs electronics : Hammett analysis Ph Br + Ar 1.5eq each Br * $+, = * #$%$ * /h%$ i 2 xh 2 (10mol%) Ligand (10mol%) Pyridine (10mol%) a (25mol%) Zn 0 (2eq) DMPU, 60ºC Br(CH 2 ) 3 C 2 Et (1eq) Ph Ar C 2 Et C 2 Et ln #$%$ 0 [#$%$] = *$ +, -,. /h%$ 0 [/h%$] + xidative addition of Ar-Br is T TF limiting xidative addition of aryl halides to i : ~ ~ 1.3 subst. L3 [i]k rel phen [i]k rel 4-H Me F Me C 2 Et CF C()Me D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

10 Preliminary Mechanistic Studies 3. Unravelling role of components : concentration variation study Br + Br C 8 H mmol each i 2 xh 2 (10mol%) Ligand 3 (10mol%) Pyridine (10mol%) a (25mol%) Zn 0 (2eq) DMPU, 60ºC C 8 H 17 - Reduction is TF determining - Ph-Br slows reaction - TMSCl, 1,2-DBE : reduction "# $ % = '( Standard Condition ) +,-. / ,-. 8 Activated Zn 2 x cat. system 2 x Zn 2 x Alkyl-Br standard 2 x Ph-Br

11 Plausible Mechanisms A. Concurrent organometallic synthesis and cross-coupling B. Disproportionation of i intermediates [i 0 ] R X 1 R 2 R [i 1 ] R 2 Transmetallation X M Y R 2 [i ] X M 0 M Y R 2 Y Direct nsertion X R 2 [i 0 ] [i ] X [i ] R 2 Y Disproportionation Metathesis R 2 [i ] [i ] X Y M 0 Reduction [i 0 ] X-M-Y R 2 Y D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

12 Plausible Mechanisms C. Sequential oxidative additions D. Radical reaction 1/2 M X 2 [i 0 ] 1/2 M 0 [i ] X R 2 Reduction Reduction X [i ] X 1/2 M 0 M XY [i 0 ] M 0 Reduction Y [i ] X X [i ] X [i ] [i ] R2 Y 1/2 M X 2 R 2 R2 or [i ] X Y R 2 Y [i V ] or R2 X Y Radical Chain D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

13 n-depth Mechanistic Studies 1. Reaction conditions 10mol% each + C 8 H 17 i(cd) 2, dtbbpy, py Mn(2eq), DMF, 60ºC Ph-C 8 H 17 Ph-Ph H 17 C 8 -C 8 H Ruling out Mechanism B : Product / Dimer vs i conc. sakada et al. : Br i(cd) 2, bipy DMF, 50~70ºC! #$ % Selectivity (Ph-C 8 H 17 vs Ph-Ph) [i] 0 X [i 0 ] [i ] X Y Disproportionation Metathesis [i ] X M 0 Reduction [i 0 ] X-M-Y R 2 [i ] R 2 R 2 [i ] Y R 2 Y S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

14 n-depth Mechanistic Studies 2.2 Ruling out Mechanism B : Stoichiometric experiment i + Et i Et DMF rt, 48h 1 : 1 1 : Evaluation of oxidative addition for C & D 3.1 Competitive experiment 1 : 1 Ph + C 8 H 17 + (bipy)i 0 (CD) 5, 10, 20, 30, 40mol% 1. DMF, rt 2. ahs 4 (aq) GC analysis to evaluate consumption rate Substrate conv (%) Ph- 89 H 17 C Reversibility experiment i Ph- (1eq) DMF, 60ºC ipr + Ph Ph ipr 65% quant. S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

15 n-depth Mechanistic Studies 3.3 Stoichiometric experiments i nc 8 H 17 - (10eq) DMF-d 7, 60ºC, 4hr C 8 H 17 ipr + (bipy)i 2 ipr quant., 99% cross-selective 2-cumyl iodide (2eq) nc 8 H 17 - (2eq) i DMF, 60ºC, 40min C 8 H 17 ipr nitial oxidative addition Ar- to i(0) ipr 56%, >99% cross-selective no dimer observed Ph- (1eq) C 8 H 17 i X generated in situ DMF, 60ºC, 1.5 / 8hr C 8 H 17 C 8 H 17 Ph C 8 H 17 X = 14 : 1 X = C 8 H : 1 S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

16 n-depth Mechanistic Studies 4.1 Evaluation of radical intermediacy for C & D : radical clock experiment DMF, 60ºC i + Br overnight + 1 : 1 none detected 56% yield 10mol% each + Br i(cd) 2, dtbbpy, py + 1 : 1 Mn(2eq), DMF, 60ºC none detected 35% yield Br + C 2 Et 97.6% ee 10mol% each i 2, dtbbpy, py Ph C 2 Et Mn(2eq), DMF, 60ºC at 10% yield remaining Alkyl-Br : 97.6% ee S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

17 Plausible Mechanisms C. Sequential oxidative additions R 2 1/2 M X 2 [i 0 ] 1/2 M 0 Reduction [i ] X X [i ] [i ] [i ] R2 Y R 2 Y R 2 radical generated & consumed at same i X 1/2 M 0 Reduction 1/2 M X 2 D. Radical reaction M 0 Y R 2 M XY [i ] X R2 or [i 0 ] Reduction [i ] X Y [i V ] or R2 X Y X [i ] Radical Chain R 2 radical generated & consumed at different i X D. J. Weix et al., J. Am. Chem. Soc., 2012, 134,

18 n-depth Mechanistic Studies 4.1 Evaluation of radical intermediacy for C & D : radical clock experiment + 5/10/15/20mol% each (dtbbpy)i 2, py Mn(2eq), TMSCl(0.04eq) DMF, 60ºC Ph Ph U R S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

19 n Summary Proposed Mechanism Mn Mn 2 (L)i 0 Ph- (L)i (L)i Ph RH 2 C- (L)i CH 2 R CH 2 R i (L) Ph Ph-CH 2 R S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

20 n Summary Proposed Mechanism Mn Mn 2 (L)i 0 Ph- (L)i (L)i Ph CH 2 R RH 2 C- (L)i CH 2 R RH 2 C- (L)i Ph Product Formation Ph-CH 2 R Ph- Ph i (L) CH 2 R (high [R ]) Ph- nitiation (low [R ]) S. Biswas and D. J. Weix, J. Am. Chem. Soc., 2013, 135,

21 ther Methodologies 1. Epoxide opening with aryl bromides i 2 xh 2 (10mol%) bipy (10mol%), py (20mol%) a (25mol%), Zn (2eq) H Ph Ph H H Br + Et 3 HCl (1eq), DMPU rt, 12hr 81% >95 : 5 icl 2 (dme) (10mol%) bipy (10mol%), Mn (2eq) H Ph Cp 2 TiCl 2 (10+4mol%) Et 3 HCl (1eq), DMPU rt, 12hr Ph 70% 1 : 3.3 H [Ti] Ar Br + Y icl 2 (dme) (10mol%) bipy (10mol%), Mn (2eq) Ti* (10mol%) Et 3 HCl (1eq), DMPU rt, 12hr Y. Zhao and D. J. Weix, J. Am. Chem. Soc., 2014, 136, Y. Zhao and D. J. Weix, J. Am. Chem. Soc., 2015, 137, Ar Y H 63~99% up to 99%ee Ti* TiCl 2 2

22 ther Methodologies 2. Coupling of aryl halides with tertiary alkyl halides R 2 R 3 2eq Br + Ar Br 1eq electron-poor i(acac) 2 (10mol%) HC (0 or 30mol%) DMAP (1eq) Ar R 2 MgCl 2 (1.5eq) R 3 Zn (2eq) DMA, rt, 12hr 39 ~ 95% ipr Cl HC ipr R 2 R 3 2eq Br + Ar 1eq electron-rich i(acac) 2 (10mol%) 3-F-py (1eq), LiCl (3eq) MgCl 2 (1.0eq), Zn (2eq) DMA, rt, 12hr Ar R 3 R 2 30 ~ 82% Me 2 C HBoc H H Bn H. Gong et al., J. Am. Chem. Soc., 2015, 137, H. Gong et al., J. Am. Chem. Soc., 2018, 140, H C 2 Me Boc H Boc H H H H Formal synthesis of (+)-Asperazine Bn

23 3. Enantioconvergent coupling ther Methodologies Ar 1 Br + Ar 2 Cl R icl 2 (dme) (10mol%) Ligand (11mol%) Mn (3eq), a (0.5eq) DMA, 0ºC, 6h R Ar 1 Ar 2 0.2mmol scale, 1 : 1 49 ~ 91% yield 88 ~ 97% ee Het + C Cl R icl 2 (dme) (10mol%) Ligand (20mol%) Mn (3eq), TMSCl (0.4eq) dioxane, rt, 18h Het C R PAr 2 Bn 0.2mmol scale, 1 : 1 41 ~ 87% yield 79 ~ 91% ee DMMB-PHX (Ar = 3,5-dimethyl- 4-methoxyphenyl) Het + S. E. Reisman et al., J. Am. Chem. Soc., 2014, 136, S. E. Reisman et al., J. Am. Chem. Soc., 2015, 137, S. E. Reisman et al., J. Am. Chem. Soc., 2017, 139, 5684 R Cl 0.2mmol scale, 1 : 1 Ar ibr 2 (diglyme) (10mol%) Ligand (20mol%) Mn (3eq), TMSCl (0.75eq) dioxane, rt, 18h R Ar Het 42 ~ 88% yield 81 ~ 94% ee C 3 H 7 C 3 H 7 C 3 H 7 BiX type Ligand C 3 H 7

24 utlook 1. Application in convergent total synthesis - Potential demonstrated in formal syntheses (Gong : (+)-Asperazine, Reisman : sertraline) 2. Further methodology development - Progress : acyl - alkyl coupling / allyl alkyl coupling alkyne alkyl coupling / multimetallic catalysis - Multicomponent reactions? Thanks for your attention!

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