Transition-metal catalyzed C C bond cleavage

Transcription

1 Transition-metal catalyzed C C bond cleavage Chaoren Shen Wanbin Group Literature Seminar

2 1.Decarboxylation(Cu Ag Pd Rh) 2. Decarbonylation(i Pd) 3. Deacylation(Pd Rh)

3 Jon A. Tunge( University of Kansas, USA ) Lukas J. Goossen( TU Kaiserslautern, Germany ) Seijiro Matsubara and Takuya Kurahashi (Kyoto University) Hideki Yorimitsu and Koichiro Oshima(Kyoto University) Andrew G. Myers (Harvard) Lei Liu(Tsinghua Univ.)

4 Decarboxylation 1. Decarboxylative Suzuki cross-coupling 2. Decarboxylative Heck reaction 3. Decarboxylative allylation 4. Decarboxylative Aldol and Mannich reaction 5. Decarboxylative Clasien rearrangement 6. Decarboxylative Michael addition

5 Advantages of carboxylic acid compound as starting material for cross-coupling: 1.large scale industrial production 2.Easy to preparation. (Molecular oxygen oxidation catalyzed by heterogeneous catalysis from sidechain aromatic compound. Water is side-product 1. High temperature 2. eed stoichiometric Mecury, Sliver or Copper 3. In system of protonic solvent, the decarboxylative intermediate is usually transformed into alkane or arene

6 Origin of Decarboxylative Suzuki cross-coupling ilsson M., Acta. Chem. Scand., 1966, 20, COOH I CuI Quinoline O 2 >250 C O 2 less than 20% aryl-copper species copper-mediated Ullmann-type coupling Lukas J. Goossen Science, 2006, 313, JACS, 2007, 129, ACIE, 2008, 47, JACS, 2008, 130, Bimetallic catalyst copper complex capable of mediating the strongly endothermic extrusion of CO2 from arenecarboxylates

7 COOH Cl 2 mol% Pd(acac) 2 6mol%iPrPPh 2 Cl 1.Addition of KF: the formation of ArC(O)OCuF seems to lower the decarboxylation barrier 2.Optimization of the steric and electronic properties of the phosphine ligand coordinated to Pd O 2 Br 1.5 eq. CuCO eq. KF MP, 120 C,24h O 2 3.azeotropic distillation/additon of molecular sieves: limiting the competing protonation of the aryl copper intermediate, Cl Cl O 2 O 2 4.the yields collapsed when most CuCO3 replaced by K2CO3, an outcome attributed to an irreversible reduction of Cu(II) to Cu(I). Clearly, an alternative protocol that is catalytic in both metals-as is required for industrial-scale applications-- would only be possible with more stable but less effective Cu(I) complexes, at the expense of an increased reaction temperature.

8 Decrease the use of 3A MS: carboxylic acid mixed with base, then heated into salt and dehydration in prior of reaction Added halide ions (which would be released in the transmetallation step) retarded this decarboxylation. the halides are in competition with the carboxylates for coordination sites at the copper. A key to achieving a general process catalytic in both metals is to induce a stronger preference of the copper for carboxylate over bromide ions by tuning its ligand environment.

9 0.3mol% CuI and 0. 06mol% Pd(acac)2 It was successfully scaled up to molar quantities at Saltigo GmbH, with 20% toluene added to adjust the solvent boiling point to 160 and allow azeotropic drying of the reaction mixture L. J. Goossen, G. Deng, patent pending, filing number PCT-DE (2005).

10 H Valsartan(Boehringer Ingelheim) O H Tasosartan (an angiotensin II receptor antagonist) O H Olmesartan O O OH O O O O O HO OH Cl H 洛沙坦 Losartan O H Irbesartan HO O Candesartan H HO O Telmisartan((Boehringer Ingelheim)) C

11 ACIE. 2010, 49, Chem. Eur. J. 2010, 16,

12 One-Pot Three-Component Decarboxylative Coupling Adv. Synth. Catal. 2011, 353,

13 ACIE, 2008, 47, JACS, 2009, 131, o addition of Cu a bulky, electron-rich ligand similar in structure to dppp

14 In I4, the Pd center is coordinatively saturated, bidentate phosphine ligands are favored forpreventing decarbonylation to form an inactive Pd-CO complex a value whose magnitude is consistent with the experimental temperature required for the reaction (ca 150 C). Decarboxylation is the rate-limiting step in the catalytic cycle.

15 copper-only system A possible explanation for the outstanding performance of diglyme is that diglyme can coordinate to K +, thereby facilitating the complexation between CuI and C 6 F 5 CO 2 - ACIE. 2009, 48, Diarylated by-products are observed

16 Decarboxylative reaction occur before oxdative addition of Cu(I) or at the stage of Cu(III)? Oxidative addition constitutes the rate-limiting step in pathway I Decarboxylation is the rate-limiting step in pathway II strong steric repulsion in the hexacoordinated species Sheppard JACS1968, 90, 2186 JACS 1970, 92,5419

17 breaking the C(sp 3 )-COOH bond: chelation-assisted activation of C(sp 2 )-C(sp 3 ) bond potassium salts of 2-(3-pyridyl)-, 2-(4-pyridyl)-, and 2-phenyl acetic acids could not undergo this coupling reaction Inspired by the recent fascinating work of Oshima et al. on chelation-assisted activation of Csp 3 -Csp 3 bond

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19 OL, 2011,13,

20 Intermolecular decarboxylative and CDC Y-M Liang, C-J Li, ACIE, 2009,48, TMEDA as ligand, TBHP as oxidant

21 F. Glourius, JACS, 2009, 131, Decarboxylation/C-H Activation 5 mol% DMSO

22 Carboxylic Acids as Traceless Directing Groups for C-H activation Igor Larrosa, ACIE, 2011, Early View DOI: /anie first meta-selective direct C-H arylation

23 Suzuki coupling: the only other straightforward approach to this important class of compounds using the corresponding meta-substituted aryl boronic acids. However, the synthesis of these starting materials generally involves several steps, which is reflected in their higher cost (ca times more expensive than the equivalent benzoic acid) 3-methoxyphenylboronic acid costs ca. 2,310 per mol, compared to 24 for the equivalent 2-methoxybenzoic acid (Aldrich) used to synthesize compound 4l

24 Which metal is responsible for decarboxylation? Pd or Ag? Hypothesis: decarboxylation of the more-hindered 3 is much faster than that of 1. Chem. Commun., 2009, Ag is not responsible for the decarboxylation step in this process

25 Pd(II) salts have only been reported to mediate the protodecarboxylation of highly electron-rich benzoic acids, whereas our system seems to be independent of the electronic nature of the initial ortho substituent. Ya-Ming Li, Chunying Duan, Synlett 2011, 12,

26 Decarboxylative Heck reaction Andrew G. Myers(Harvard) JACS,2002,124, OL, 2004, 6, JACS, 2005, 127, decarboxylative or ortho-palladation reaction 5% DMSO-DMF: DMSO-Pd complex The evolutionof CO 2 (precipitate formed in lime water) The disappearance of resonances associated with 1a Peaks for a new intermediate with arene resonances upfield of those of 1a, Qunched by styrene with simultaneous precipitation of a solid presumed to be Pd(0)

27 Jin-Heng Li, OL, 2009,

28 Decarboxylative Michael addition Pinjing Zhao (CSU) Angew. Chem. 2009, 121,

29 Decarboxylative Aldol and Mannich reaction M. Shair (Harvard), JACS, 2003, 125, M. Shibasaki JACS, 2009,131,

30 Decarboxylative Clasien rearrangement Craig( Imperial College London ) OL, 2005,5: ACIE, 2005, 44, Chem. Commun., 2008,

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