Anti-Markovnikov Olefin Functionalization

Transcription

1 Anti-Markovnikov Olefin Functionalization ~Prof. Robert H. Grubbs Work~ 4 th Literature Seminar July 5, 2014 Soichi Ito (D1)

2 Contents 1. Introduction Flow of Prof. Grubbs Research Markovnikov s Rule Wacker Oxidation 2. Grubbs Work Substrate-Controlled Wacker Oxidation Catalyst-Controlled Wacker-Type Oxidation 2

3 Introduction ~Flow of Research~ Olefin Metathesis Anti-Markovnikov Wacker Oxidation of Terminal Olefin Z-Selective Metathesis Ethenolysis Wacker Oxidation of Internal Olefin Substrate-Controlled Hydration + Reduction Hydroamination Z-Selective Ethenolysis Catalyst-Controlled Decarbonylative Dehydration Hydrophosphonation Production of Terminal Olefin Functionalization of Terminal Olefin 3

4 Introduction ~Markovnikov s Rule~ Two-Step Two-Step (+1C) Robert H. Grubbs et al. Science, 2011, 333,

5 One-Step Anti-Markovnikov Hydration of Olefins This work was difficult to reproduce. One-Step with Activated Olefins William C. Trogler et al. Science 1986, 233, Inorg. Chem. 1988, 27, Robert G. Bergman and F. Dean Toste et al. J. Am. Chem. Soc. 2003, 125, Three-Step Ben L. Feringa and Gerard Roelfes et al. Nat. Chem. 2010, 2, 991. Shannon S. Stahl et al. J. Am. Chem. Soc. 2010, 132,

6 Anti-Markovnikov Wacker Oxidation / Reduction Strategy 6 Robert H. Grubbs et al. Science, 2011, 333, Oxidation cycle must be compatible with the reduction cycle. aldehyde-selective Wacker Oxidation

7 Terminal alkenes may be viewed as masked ketones. 7 Jacques Muzart Tetrahedron 2007, 63, Introduction ~Wacker-Tsuji Oxidation~ 1894 F. C. Phillips reported stoichiometric reaction J. Smidt et al. reported the Wacker process. (oxidation of ethylene to acetaldehyde) Investigations for convenient laboratory methods 1976 J. Tsuji et al. reported PdCl 2, CuCl / DMF, H 2 O method.

8 DMF / H 2 O System CuCl 2 tends to chlorinate ketones. Jiro Tsuji et al. Tetrahedron Lett. 1976, DMSO, acetone, AcOH, THF, dioxane, MeCN were not good. Charles M. Selwitz et al. J. Org. Chem. 1964, 29,

9 Development: Direct O 2 -Coupled Wacker Oxidation Ligand : Roger A. Sheldon et al. Chem. Commun. 1998, Kiyotomi Kaneda et al. Angew. Chem. Int. Ed. 2006, 45, 481. Pd[(-)-sparteine]Cl 29 Matthew S. Sigman et al. Org. Lett. 2006, 8, 4117.

10 Selectivity of Wacker Oxidation With directing group Catalyst-controlled selectivity is required. Robert H. Grubbs et al. J. Am. Chem. Soc. 2014, 136,

11 Anti-Markovnikov Wacker Oxidation Strategies with Directing Groups with Stoichiometric Palladium or Excess Heteropolyacid Ben L. Feringa et al. J. Am. Chem. Soc. 2009, 131, rt Other Pd(ll) such as Pd(OAc) 2 and Pd(NO 3 ) 2 gave exclusively the methyl ketone. Aromatic group was crucial. Jonathan B. Spencer et al. Chem. Eur. J. 2006, 12,

12 Catalyst-Controlled (or Solvent-Controlled?) Jacques Muzart Tetrahedron 2007, 63, Ben L. Feringa J. Chem. Soc., Chem. Commun. 1986, 909.? 12

13 Timothy T. Wenzel J. Chem. Soc., Chem. Commun. 1993, 862. (1 mmol) Similar Trends No Isomerization High Selectivity Low Yield The use of LiCl and/or CuCl reduced the regioselectivity. Takahiro Hosokawa et al. Bull. Chem. Soc. Jpn. 2005, 78,

14 Ketone-Selective Wacker-Type Oxidation Catalyst-Controlled!! Matthew S. Sigman et al. J. Am. Chem. Soc. 2009, 131, Matthew S. Sigman et al. J. Am. Chem. Soc. 2011, 133, Matthew S. Sigman et al. Acc. Chem. Res. 2012, 45,

15 Contents 1. Introduction Flow of Prof. Grubbs Research Markovnikov Rule Wacker Oxidation 2. Grubbs Work Substrate-Controlled Wacker Oxidation Catalyst-Controlled Wacker-Type Oxidation 15

16 General Reaction Scheme about Shvo s catalyst, see: Chem. Rev. 2010, 110, Control Experiments 16

17 Substrate Scope Major Byproduct 17

18 Triple Relay Catalysis System Proposed Mechanism Initial Mechanistic Study without H 2 O, IPA, Shvo s cat. enol ether hydrolysis D 2 O Shvo s cat. 18

19 Aldehyde Selective Wacker Oxidation under aerobic condition 19 Robert H. Grubbs et al. Org. Lett. 2012, 14, 3237.

20 Aldehyde Selective Wacker Oxidation because of the increase in acidity? The bulkiness of t-buoh is important for aldehyde-selectivity. Product yield starts decreasing likely due to self-condensation. 20

21 Catalyst-Controlled Wacker-Type Oxidation Without t-buoh (only MeNO 2 ), no conversion was observed. Entry 1 Entry 2 Robert H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52,

22 Detailed Yield & Selectivity Entry 1 Entry 2 22

23 Substrate Scope With styrene Intermolecular Markovnikov Attack + Hydrolysis H Aldehyde-Selective Wacker Oxidation on a 10 mmol Scale with Reduced Catalyst Loading 23

24 Comparison of Innate Selectivity without assistance from a Thorpe-Ingold effect 24

25 Influence of PhO-Proximity 25 Robert H. Grubbs et al. J. Am. Chem. Soc. 2014, 136, 890.

26 Influence of Oxygen Functionality aldehyde / ketone Catalyst-Controlled Regioselectivity 26

27 Influence of Steric Profile 5 h 24 h 24 h 5 h 24 h 27

28 Applicability of Nitrate-Modified Wacker Oxidation On a Larger Scale Synthesis of Atomoxetine Retention of Stereochemical Information Drug for the treatment of ADHD about Ir catalyst, see John F. Hartwig et al. J. Am. Chem. Soc. 2003, 125,

29 Preliminary Mechanistic Insight Stoichiometric 18 O-Labeling Experiment Plausible Mode of Oxygen Transfer Brief induction period The same catalytic species remains active. 29 Robert H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52,

30 Oxidation of Olefins with Nitro-Nitrosyl Redox Couple Transition-Metal Nitro-Nitrosyl Redox Coupling color: orange yellow detectable at least 1 h ketone selective Grubbs system 30 Mark A. Andrews et al. J. Am. Chem. Soc. 1981, 103, 2894.

31 Metal Nitro Complexes as Catalysts Mark A. Andrews et al. Organometallics 1984, 12, we believe far less likely

32 Nitration of Alkenes by Palladium Nitro Complexes Mark A. Andrews et al. Organometallics 1984, 3, Path 1: cis Path 2: trans support trans

33 Preliminary Mechanistic Insight Radical Model to Explain Anti-Markovnikov Selectivity Influence of Electronic Properties Robert H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52, electron-deficient Robert H. Grubbs et al. J. Am. Chem. Soc. 2014, 136,

34 Compared with Cationic Transition State Intermolecular Competition Experiments electron-deficient Intramolecular Competition Experiments Robert H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52,

35 Preliminary Mechanistic Insight Is NO 2 generated? in a sealed vessel (air) NO 2 (gas) flies away? When the reaction is run in an unsealed vessel, significantly lower yield and selectivity is observed. What mediates NO 2 delivery? Stoichiometric reaction of CuCl 2 and AgNO 2 with an alkene (without Pd) gave no conversion of alkene. Pd may mediate NO 2 delivery. One-pot Intermolecular Competition Experiments Without metal Robert H. Grubbs et al. J. Am. Chem. Soc. 2014, 136, 890. William A. Pryor et al. J. Am. Chem. Soc. 1982, 104,

36 cf. Plausible Mechanism of Radical Nitration 36 Hiroyuki Ishibashi et al. Adv. Synth. Catal. 2011, 353, 2643.

37 Mechanism? about hydrolysis of alkyl nitrite, Michael P. Doyle et al. J. Org. Chem. 1983, 48,

38 Summary slide 14 Robert H. Grubbs et al. J. Am. Chem. Soc. 2014, 136, 890. Styrene-type substrate 38 Robert H. Grubbs et al. Org. Lett. 2012, 14, 3237.

39 Appendix 39

40 Intermediates in the Autoxidation of Nitrogen Monoxide detected with EPR 40 Williem H. Koppenol et al. Chem. Eur. J. 2009, 15, 6161.

41 cf. Nitration of Olefins with AgNO 2 and TEMPO AgNO 2 (3 eq) TEMPO (0.4 eq) MS4A, DCE 41 Debabrata Maiti et al. J. Am. Chem. Soc. 2013, 135, 3355.

42 cf. Nitrate as a Redox Co-Catalyt 25 mol% NaNO 3 Known Reaction 42 Melanie S. Sanford et al. Chem. Sci. 2012, 3, 3192.

43 Other Olefin Functionalizations Hydroamination Wacker Oxidation / Transfer Hydrogenative Reductive Amination Two-Step, One-Pot Hydroamination Protocol see: Robert H. Grubbs et al. Chem. Sci. 2014, 5, 101. Wacker Oxidation of Internal Olefins see: Robert. H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52, Robert H. Grubbs et al. Angew. Chem. Int. Ed. 2013, 52, Hydrophosphonation see: slide 44,45 Robert H. Grubbs et al. Org. Lett. 2011, 13, Pd-Catalyzed Decarbonylative Dehydration of Fatty Acids see: slide 46~49 Robert H. Grubbs, Brian M. Stoltz et al. Adv. Synth. Catal. 2014, 356,

44 Precedent : Radical Cyclization HWE Reactions Hydrophosphonation James G. T. Rawlinson et al. Org. Lett. 2005, 7, Robert H. Grubbs et al. Org. Lett. 2011, 13,

45 Hydrophosphonation 45

46 Pd-Catalyzed Decarbonylative Dehydration of Fatty Acids High Temperature Process (Miller, Kraus) volatile olefins only Low Temperature Process (Gooβen, Scott) Grubbs Work Robert H. Grubbs, Brian M. Stoltz et al. Adv. Synth. Catal. 2014, 356,

47 Effect of Catalyst, Ligand, and Additive 47

48 Portionwise Addition of Acetic Anhydride Large-Scale Decarbonylative Dehydration stearic acid 10-acetoxydecanoic acid 48

49 Substrate Scope 49