Mn Reagent & Organomanganese: Neglected Powerful Tool. Reporter: Li Zhuo Advisor: Prof. Yang Prof. Chen Prof. Tang

Transcription

1 Mn Reagent & Organomanganese: Neglected Powerful Tool Reporter: Li Zhuo Advisor: Prof. Yang Prof. Chen Prof. Tang 1

2 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 2

3 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 3

4 Introduction 25 VII B Mn [Ar]3d 7 4s Manganese, Mn Named by Magnes, Magnetic Discoverer: 1774, Johann Gahn Silver-gray metal, Mohs hardness = ppm in earth crust (lower than Fe, Ti) Single nuclide in nature Oxidation state: -3, -2, -1, 0, 1, 2, 3, 4, 5, 6, 7 4 Mn Metal Mn(AcAc) 3 KMnO 4

5 Introduction Low valence: Middle valence: High valence: Bond type: -3, -2, -1, 0, +1 [Ar]3d 5 4s 2 Mn-CO, Mn-X, Mn-olefin +2, +3 [Ar]3d 5 Mn-O, Mn-N=R, Mn-X +4, +5, +6, +7 [Ar]3d 3 Mn=O, Mn=N-R, Mn-X Reaction mechanism: Radical (heat); Typical Compounds: 5 Carbonylation (neat r.t.) Mn(-3): Na 3 [Mn(CO) 4 ] Mn(-2): Na 2 [Mn(CO) 5 ] Mn(-1): Mn(CO) 5 COR Mn(0): Mn 2 (CO) 10 Mn(+1): Mn(CO) 5 X X = Halogen, OAc,OTf et al. Radical (Mn(III)); Nucleophilic (Mn(II)); Radical (MnR 2 ) Mn(+2): MnX 2, Mn(dpm) 2, Mn(AcAc) 2 et al. Mn(+3): Mn(O 2 CR) 3, Mn(dpm) 3 Mn(AcAc) 3 et al. Nucleophilic Oxidation Mn(+4): MnO 2 Mn(+5): [Mn(Salen)=O]X, K 3 MnO 4 Mn(+6): K 2 MnO 4 Mn(+7): KMnO 4, MnO 3 F, Mn 2 O 7

6 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 6

7 Oxidation by Mn(VII): in aqueous solution Mn(VII): KMnO 4, Mn 2 O 7, MnO 3 F Confirmed by spectroscopy 7 Mishra, B. K. et al. Tetrahedron, 2009, 707

8 Oxidation by Mn(VII): in organic solution Cosolvent: t-buoh, Acetone, Pyridine, AcOH, Ac 2 O, CF 3 CO 2 H Phase-transfer catalyst: crown ether, crypt ether, R 4 NX D. J. Sam, 1972: [18C6-K] + [MnO 4 ] - - PhH solution: Purple Benzene, 0.06M in PhH 8 Mishra, B. K. et al. Tetrahedron, 2009, 707

9 Oxidation by Manganese dioxide Perparation: MnO Mn 2+ = γ-mno 2 (activated), fliter, dry at 100 Brown precipate Mechanism: Example: 9 Soldatova, S. A. et al. Chem. Hetero. Com. 2009, 633

10 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 11

11 Mn(Salen)=O: conformation & reaction M. Komatsu, 2002: Example: 12 Katsuki, T. Adv. Synth. Catal., 2002, 131

12 Mn(Salen)=O: conformation & reaction M. Komatsu, 2002: Example: 13 Katsuki, T. Adv. Synth. Catal., 2002, 131

13 Reduced Porphyrinogen ligand: a new direction R. Neier, 2012: [MnLOAc] + OAc - [MnLCl] + Cl - 14 Neier, R. et al. Adv. Synth. Catal., 2012, 428

14 Cycloproponation by Mn(V)=N M. Nishimura, 2002: Mechanism: 15 Komatsu, M. et al. J. Org. Chem., 2002, 2101.

15 Oxazolination by Mn(V)=N M. Nishimura, 2002: Route b: 16 Komatsu, M. et al. J. Org. Chem., 2002, 2101.

16 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 17

17 Catalytic radical oxidation by Mn(III) Alkane: R = -O 2 CCH 2 PO 3 Na 2 18 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

18 Catalytic radical oxidation by Mn(III) Alcohol & Aldehyde: Mn(II) as catalyst precuesor: Generate Mn(O 2 CR) 3 in situ 19 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

19 Catalytic oxidation by Mn(III) Sulfide: RCHO as assistant reductant: 20 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

20 Catalytic radical reaction by Mn(III) O 2 -RSiH 3 Initiator-reductant system: Markovnikov product Chiral Version: 21 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

21 Catalytic radical oxidation by Mn(III) E. M. Carreira, 2006: Hydrohydrazination reaction: 22 Carreira. E. M. et al. J. Am. Chem. Soc., 2006,

22 Catalytic oxidation by Mn(III) Reaction scope: 23 Carreira. E. M. et al. J. Am. Chem. Soc., 2006,

23 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 24

24 Preperation of Organomanganese(II) 1) Transmetalation in Et 2 O/THF The only problem is to prepare the corresponding Grignard reagent or organolithium. 2) Oxidation additive of RX to Mn R. D. Rieke, 1972: The resulting active Mn is one of the most reactive metal undergos oxidative addition with some of unreactive halides. 25 Cahiez, G. et al. Chem. Rev., 2009, 1434.

25 Organomanganese(II): tolerance & stability Tolerance: Stability: 26 Cahiez, G. et al. Chem. Rev., 2009, 1434.

26 Addition to carbonyl group: activity & selectivity Activity: Organomanganese(II) act as a soft Grignard reagent (include CO 2, SO 2 ), but do not add to Nitrile, Ester, Amide. Selectivity: 27 Cahiez, G. et al. Chem. Rev., 2009, 1434.

27 Addition to acyl chloride: a comparison MnRX addition: Fukuyama Coupling: Cheap Low temperature shorter time Simple system Expensive High temperature longer time Complicated system Fit for multi-step synthesis 28 Cahiez, G. et al. Chem. Rev., 2009, 1434.

28 Reaction with gem-dibromo compound 29 Oshima, K. J. Organomet. Chem., 1999, 1.

29 Addition to unactivated multiple bond General formula: Addition to Triple bond: Addition to double bond: 30 Cahiez, G. et al. Chem. Rev., 2009, 1434.

30 Cross-coupling catalysis by Mn(II)/(III) Stille-Type: Kumada-Type: Homocoupling: 31 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

31 Other reactions 1,4-addition (without Cu(I)): Transmetalation then nucleophilic attack Also occur when substance is α,β-unsaturated ester & aldehyde 32 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

32 Other reactions Mn(II) act as Lewis Acid: Addition to nitroolefin: 33 Dzhemilev, U. et al. Russ. J. Org. Chem., 2012, 309.

33 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 34

34 Low Valence Manganese compound Mn(-3): Na 3 [Mn(CO) 4 ] (unuseful in Org. Chem.) Mn(-2): Na 2 [Mn(CO) 5 ] Mn(-1): Mn(CO) 5 COR Mn(0): Mn 2 (CO) 10 Mn(I): Mn(CO) 5 X, X = Halogen, OAc,OTf et al. Mn 2 (CO) 10 : First synthesis in 1949 Gold-yellow solid, stable in air, Unsoluble in H 2 O, soluble in Org. 35

35 Low Valence Manganese: reaction Mn 2 (CO) 10 : A radical catalyst over 100, uesd in olefin telomerization/chlorination reaction. As carbonylation catalyst: 36 Calderazzo, F., Inorg. Chem., 1965, 293. Snieskus, V. et al. J. Org. Chem., 1986, 273.

36 Low Valence Manganese: reaction MnBr(CO )5 : A π-acid, coordinate with alkene & alkyne. K. Takai, 2008: [2+2+2] K. Takai, 2010: 37 Takai, K. et al. Org. Lett., 2008, Takai, K. et al. J. Org. Chem., 2010, 334.

37 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical reaction by Mn(III) Nucleophilic reaction by Mn(II) Low valence Mn Summary Acknowledgement 38

38 Summary Low valence: Middle valence: High valence: -3, -2, -1, 0, +1 [Ar]3d 5 4s 2 +2, +3 [Ar]3d 5 +4, +5, +6, +7 [Ar]3d 3 Radical (heat); Carbonylation (neat r.t.) Radical, Transmetalization, Nucleophilc addition. Nucleophilic/Radical Oxidation 39

39 Summary Substance & reaction Synthon Advantage C=C C=O C-H 1. Oxidation 2. Grignard reagent Addition 3. Hydration Nuc. Addition 2. Carbonylation Oxidation 2. Cheap Low temperature shorter time Simple system Enviornmentally friendly C-X 1. Oxi. Addition 2. Cross-Coupling 3. 40

40 Acknowledgement Prof. Yang, Prof. Chen, Prof. Tang Mr. Shouliang Yang Mr. Zhiyao Zhou Lab. 630 Evereyone here 41