Streamlining Reaction Discovery and Development Through Kinetic Analysis

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1 Streamlining Reaction Discovery and Development Through Kinetic Analysis R 3 Si X Ni(0) Ligand R 3 Si X [Substrate] 0 0 Time J. Am. Chem. Soc. 2011, 133, 5728 Professor Ryan D. Baxter

2 utline: Direct Comparison of Initial Rates vs. Reaction Progression "Ynal" R 3 Si X Ni(0) Ligand R 3 Si X CF 3 H C 2 K R Pd(II)-cat. Ligand CF 3 C 2 K R D[Ynal] Initial Rates, Dt verlay» Relative Rates [Ynal] (mol/l) [Substrate] Time (seconds) Time (minutes) - rder in [ynal], [silane], [Ni] - 30 experiments - rder in [substrate], [olefin], [Pd] - Catalyst stability, product inhibition, relative binding constants - 12 experiments

3 Nickel Catalyzed Reductive Couplings (Montgomery Group, 2010)

4 Distinguishing Between Mechanistic Possibilities - Crossover experiment probes cleavage of Si H/D bond - Silane scrambling seems to be ligand-dependent - Mechanism for silane? (1) L n Ni(0) Ni Et 3 Si-H Et 3 Si H (2) Et 3 Si-H Ni(0) L n Ni H SiEt 3

5 In Situ Monitoring of Aldehyde/Alkyne Couplings "Ynal" + Et 3 Si-H 10% Ni(CD) 2 20% PCy 3 Et 3 Si THF (0.1 M) -25 o C 1.0 equiv 2.0 equiv 86% H Et 3 Si X X = D, 90% X = H, 10% Pr 3 Si X X = D, 11% X = H, 89% ~10% crossover with PCy 3

6 In Situ Monitoring of Aldehyde/Alkyne Couplings "Ynal" + Et 3 Si-H 10% Ni(CD) 2 20% PCy 3 Et 3 Si THF (0.1 M) -25 o C 1.0 equiv 2.0 equiv 86% H Et 3 Si X X = D, 90% X = H, 10% Pr 3 Si X X = D, 11% X = H, 89% ~10% crossover with PCy 3

7 Rate Dependence on Catalyst Concentration "Ynal" + Et 3 Si-H X% Ni(CD) 2 2X% PCy 3 Et 3 Si THF (0.1 M) -25 o C H 1.0 equiv 2.0 equiv [Ynal]/ time (M/s) * [Ynal](mol/L) mol% Ni(CD)2 15 mol% Ni(CD)2 20 mol% Ni(CD)2 25 mol% Ni(CD) [Ni(CD) 2 ] (mol/l) Time (seconds)

8 Rate Dependence on Substrate Concentration "Ynal" + Et 3 Si-H 10% Ni(CD) 2 20% PCy 3 Et 3 Si THF (0.1 M) -25 o C H equiv 2.0 equiv 12 D [Ynal]/ D time (M/s) * [Ynal] (mol/l) [Ynal] (mol/l) Time (seconds)

9 Rate Dependence on Silane Concentration "Ynal" + Et 3 Si-H 10% Ni(CD) 2 20% PCy 3 Et 3 Si THF (0.1 M) -25 o C H 1.0 equiv equiv [Ynal]/ time (M/s) * [Ynal] (M) M Et3SiH 0.2 M Et3SiH 0.3 M Et3SiH 0.4 M Et3SiH [Et 3 SiH] (mol/l) Time (seconds)

10 Role of Silane in Reductive Coupling H (1.0 equiv) + Et 3 Si-H Et 3 Si-D 10% - Ni(CD) 2 Et 3 Si 20% - PCy 3 THF (0.1M, 45 o C) H/D (3.0 equiv each) H/D = 50:50 KIE = 1.00 No observable kinetic isotope effect FIRST-RDER FIRST-RDER L n Ni(0) Ni rate-determining Et 3 Si-H fast ZER-RDER 100 mol% Ni/PCy 3 added But what about crossover?!

11 A Tale of Two Catalytic Cycles products without crossover H products with crossover Et 3 Si H L n Ni II Ni(0)L n Ni H L n Ni(0)L n L n Ni II H SiEt 3 + Pr 3 Si H L n Ni II Et 3 Si-H L n Ni II L Ni Ni L SiEt 3 Ni L H Ni Pr 3 Si-H Et 3 Si-H J. Am. Chem. Soc. 2014, 136, 17495

12 Summary of Nickel-Catalyzed Reductive Coupling "Ynal" + Et 3 Si-H 10% Ni(CD) 2 20% PCy 3 Et 3 Si THF (0.1 M) -25 o C 1.0 equiv 2.0 equiv 86% H Et 3 Si X X = D, 90% X = H, 10% Pr 3 Si X X = D, 11% X = H, 89% ~10% crossover with PCy 3 [Ynal] (mol/l) D[Ynal] Initial Rates, Dt - rder in [ynal], [silane], [Ni] - 30 experiments - 1/2 of a.d Time (seconds)

13 Traditional Kinetic Analysis: Initial Rates catalyst A + B C - A large excess of B ensures a small change in concentration during the first portion of the reaction (~10%) - The majority of the acquired data is not factored into rate 0.12 [Ynal] (mol/l) [A] Initial Rates, D[A] Dt D[A]/Dt * Time Time (seconds) [A] (mol/l)

14 Traditional Kinetic Analysis: Initial Rates catalyst A + B C - A large excess of B ensures a small change in concentration during the first portion of the reaction (~10%) - The majority of the acquired data is not factored into rate 0.12 [Ynal] (mol/l) [A] Initial Rates, D[A] Dt D[A]/Dt * Time Time (seconds) [A] (mol/l)

15 Traditional Kinetic Analysis: Initial Rates catalyst A + B C - A large excess of B ensures a small change in concentration during the first portion of the reaction (~10%) - The majority of the acquired data is not factored into rate 0.12 [Ynal] (mol/l) [A] Initial Rates, D[A] Dt straight into the garbage! D[A]/Dt * Time Time (seconds) [A] (mol/l)

16 Traditional Kinetic Analysis: Initial Rates catalyst A + B C - A large excess of B ensures a small change in concentration during the first portion of the reaction (~10%) - The majority of the acquired data is not factored into rate 0.12 [Ynal] (mol/l) [A] Initial Rates, D[A] Dt D[A]/Dt * 10-5 note [A] 0 for a subsequent reaction Time Time (seconds) [A] (mol/l)

17 Traditional Kinetic Analysis: Initial Rates catalyst A + B C - A large excess of B ensures a small change in concentration during the first portion of the reaction (~10%) - The majority of the acquired data is not factored into rate 0.12 [Ynal] (mol/l) [A] Initial Rates, D[A] Dt D[A] Dt D[A] Dt D[A] Dt D[A] Dt D[A]/Dt * 10-5 note [A] 0 for a subsequent reaction Time Time (seconds) [A] (mol/l)

18 Reaction Progress Kinetic Analysis (RPKA) catalyst A + B C - Reagents A and B are present in synthetic concentrations - As A reacts with B, the concentration difference between them should remain unchanged - EXCESS: [A] 0 - [B] 0 [Ynal] (mol/l) [A] [A] 0 = 0.10 M, [B] 0 = 0.15 M excess = 0.05 M Conversion [A] (mol/l) [B] (mol/l) excess Time Time (seconds) now we can compare data from experiments where both A and B are changing synthetic conditions!

19 Reaction Progress Kinetic Analysis (RPKA)

20 C-H Activation of Arylacetic Acids ~ 30-fold rate increase with amino acid ligands

21 C-H Activation of Arylacetic Acids IR NMR ReactIR TM 45M fitted with a dicomp ATR probe - absorbance data converted directly to concentration - NMR calibration confirmed IR measurement of reaction progression with Dave Sale,.D.

22 C-H Activation of Arylacetic Acids: Same Excess

23 C-H Activation of Arylacetic Acids: Same Excess - The values of [1] and [2] will coincide when reaction a) is at 50% conversion and reaction b) is at 0% conversion - Look for graphical overlay

24 C-H Activation of Arylacetic Acids: Same Excess - The values of [1] and [2] will coincide when reaction a) is at 50% conversion and reaction b) is at 0% conversion - Look for graphical overlay

25 C-H Activation of Arylacetic Acids: Same Excess, Product Added - The values of [1] and [2] will coincide when reaction a) is at 50% conversion and reaction b) is at 0% conversion - Look for graphical overlay

26 C-H Activation of Arylacetic Acids: Same Excess, Product Added - The values of [1] and [2] will coincide when reaction a) is at 50% conversion and reaction b) is at 0% conversion - Look for graphical overlay

27 C-H Activation of Arylacetic Acids: Different Excess

28 C-H Activation of Arylacetic Acids: Different Excess

29 C-H Activation of Arylacetic Acids: Different Excess

30 C-H Activation of Arylacetic Acids: Different Excess

31 C-H Activation of Arylacetic Acids: Different Excess

32 C-H Activation of Arylacetic Acids: Different Excess

33 Piecing Together the Mechanistic Puzzle: Driving Forces

34 Piecing Together the Mechanistic Puzzle: Driving Forces

35 Piecing Together the Mechanistic Puzzle: ff Cycle Catalyst Binding CF 3 2b Ac K Pd C 2 n-hex HN PG R' K eq,2b Negative rder in 2 CF 3 Ac K H PG N Pd R' K eq,3b Negative rder in Product CF 3 K R Pd Ac 3b C 2 n-hex HN PG R' R = arylacetic acid product binding is stronger that substrate binding!

36 Piecing Together the Mechanistic Puzzle: Role of the Ligand

37 Piecing Together the Mechanistic Puzzle: Role of the Ligand favored for C-H activation

38 Summary of C-H Activation of Arylacetic Acids

39 Summary: Initial Rates vs. Reaction Progression "Ynal" R 3 Si X Ni(0) Ligand R 3 Si X CF 3 H C 2 K R Pd(II)-cat. Ligand CF 3 C 2 K R D[Ynal] Initial Rates, Dt verlay» Relative Rates [Ynal] (mol/l) [Substrate] Time (seconds) Time (minutes) - rder in [ynal], [silane], [Ni] - 30 experiments - rder in [substrate], [olefin], [Pd] - Catalyst stability, product inhibition, relative binding constants - 12 experiments

40 Acknowledgements Nickel Chemistry M. Taylor Haynes,. D. Professor John Montgomery* Palladium Chemistry David Sale,. D. Keary M. Engle,. D. Professor Jin-Quan Yu Professor Donna G. Blackmond*

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