Investigations of Organocuprates
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1 Investigations of rganocuprates Department of Chemistry University of North Carolina at Charlotte Andy Thomas
2 Rapid injection NMR Why is RINMR so useful? Time intervals between spectra can be modified to fit the reaction profile. Integration feature along with an internal standard is a convenient tool for kinetic and quantitative studies. Nitrogen cooling allows for low temperature experimentation. Nitrogen cooling/heating also provides an environment similar to a chlenk flask. Allows for the preparation, characterization and subsequent reaction of unstable intermediates! Rapid injection NMR: a simple technique for the observation of reactive intermediates. McGarrity, Prodolliet & myth rganic Magnetic Resonance (1981), 17(1),
3 The RI-NMR setup
4 Copper Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction -andmeyer reaction -Glaser reaction organocuprate reactions: -Alkylation reaction -Allylation reaction -Conjugate addition reaction
5 Copper 2 R Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction R R -andmeyer reaction Br! -Glaser reaction organocuprate reactions: -Alkylation reaction -Allylation reaction -Conjugate addition reaction Ullmann, F. Ber. Dtsch.Chrm. Ges. 1903, 36, 2382
6 Copper Biology: Found in metalloenzymes R rganic ynthesis: organocopper reactions R -Ullmann reaction CN -andmeyer reaction N + 2! CN -Glaser reaction organocuprate reactions: -Alkylation reaction -Allylation reaction -Conjugate addition reaction andmeyer, T. Ber. Dtsch.Chrm. Ges. 1884, 17,
7 Copper 2 R Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction -andmeyer reaction -Glaser reaction 2 Cl 2 NH 3 (aq), EtH / 2 R R organocuprate reactions: -Alkylation reaction -Allylation reaction -Conjugate addition reaction Glaser, C F. Ber. Dtsch.Chrm. Ges. 1869, 2,
8 Copper Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction -andmeyer reaction -Glaser reaction CH 3 Gilman Reagent I CH CH 3 3 (CH 3 ) 2 organocuprate reactions: -Alkylation reaction I -Allylation reaction -Conjugate addition reaction Gilman, H., Jones R. G., Woods, L. A., J. rg. Chem. 1952, 17, 1630
9 Copper Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction -andmeyer reaction -Glaser reaction CH 3 Gilman Reagent I CH CH 3 3 THF (CH 3 ) 2 organocuprate reactions: -Alkylation reaction I -Allylation reaction -Conjugate addition reaction H 3 C THF X H 3 C THF THF. H. Bertz, R. A. J. mith, J. P. nyder, and A.. Vellekoop, rganometallics 1995, 1213
10 I Ac Copper Biology: Found in metalloenzymes rganic ynthesis: organocopper reactions -Ullmann reaction R R 2 -andmeyer reaction -R -Glaser reaction R 2 -R R organocuprate reactions: -Alkylation reaction -Allylation reaction -Conjugate addition reaction R 2 -R R House, H.., Respess, W.L., Whitesides, G.M., J. rg. Chem. 1966, 31, 3128 Corey, E.J., Posner, G.G., J. Am. Chem. oc. 1968, 89, 3911
11 Alkylation Reaction Bertz,.H., Cope,., Dorton, D. Murphy, M., gle, C.A., Angew. Chem. Int. Ed. 2007,46, Bartholomew, E.R.; Bertz,.H.; Cope,.K.; Dorton, D., Murphy, M.D.; gle; C.A. Commun. 2008,
12 Product of CH 3 13 CH 2 I with ( 13 CH 3 ) 2 I/PBu 3 2 J trans ( 13 C 31 P) = Hz 2 J cis ( 13 C 31 P) = 14.6 Hz CH 3 CH !0.06 CH 3! + PBu 3 CH 3 31 P NMR spectrum of CH 3 13 CH 2 ( 13 CH 3 ) 2 (PBu 3 ) Bartholomew, Erika R.; Bertz, teven H.; Cope, tephen; Dorton, Donna C.; Murphy, Michael; gle, Craig A. Neutral organocopper(iii) complexes. Chemical Communications (2008),
13 Allylation Reaction
14 Cl Cl 2 2 H 2 C C CH 2 Bartholomew, E.R.; Bertz,.H.; Cope,.K.; Murphy, M.D.; gle; C.A.; Thomas, A.A. Chem. Commun. 2010, 46,
15 Preparation of ( 13 CH 3 ) 4 Fully couple 13 C NMR spectrum of ( 13 CH 3 ) 4 Erika R. Bartholomew, teven H. Bertz, tephen K. Cope, Michael D. Murphy, Craig A. gle and Andy A. Thomas, Chemical Communications, 2010, 46,
16 Reactions of (CH 3 ) 4 : Reactivity of Copper(III) CH 3! CH 3 CH 3 + C(CH 3 ) 3 + CH 4 C(CH 3 ) 3 H N CH 3! CH 3 N CH 3 N + + CH 4 H N CH 3! CH 3 CN CH CH 3 Br BrCN CH 3! CH 3 CH 3 CH 3 + CH 3 H No RXN at -100 C Ph 2 P Ph 2 PH C 2 CH 3! CH 3 + CH 3 PPh 2 No RXN at -100 C Bartholomew, E.R.; Bertz,.H.; Cope,.K.; Murphy, M.D.; gle; C.A.; Thomas, A.A. Chem. Commun. 2010, 46,
17 Cl Cl 2 2 H 2 C C CH 2 2 Bartholomew, E.R.; Bertz,.H.; Cope,.K.; Murphy, M.D.; gle; C.A.; Thomas, A.A. Chem. Commun. 2010, 46,
18 1 H NMR of 13 C # + " 13 C! Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
19 1 H NMR of 13 C C NMR Coupling Constants J cis = 4 Hz J trans = 28 Hz # + " 13 C! Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
20 Complexes with thioketones (M =, ) Ph " + Ph! Ph " M + Ph " + " ! M Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
21 Complexes with dithioesters (M =, ) F 3 C ! Ph! Ar 1! Ar 2! " M + " M + Ph Ar 1 Ar 2 " M + " M + Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
22 tructures of substrates, complexes and addition products " +! " M " +! " M + N X N " + Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
23 Complexes with isothiocyanates N C C N! + " N! M + N C n/d Ph C N! Ph C N! + Bertz,.H.; Moazami, Y., Murphy, M.D.; gle, C.A.; Richter, J.D. Thomas, A.A. J. Am. Chem. oc. 2010, 132,
24 RI-NMR of 2 /I with phenyl isothiocyanate n/d C Ph N CH 3 CH Time!100 o C, THF-d C Ph N CH 3 CH
25 Displacement reactions C # + # + "! C 2
26 Displacement reactions C # + # + "! C 2 > > > > C 2 F 3 C NC CN NC CN NC CN > > > NC CN Ph > > > Ph Ph
27 Conjugate Addition Reaction Pathway Homocuprate ( ) 2 TMCl TM TM = CH 3 xidative Addition Nu Nu! -Nu( ) Reductive Elimination TM
28 1 H spectra of! 3 and! 2 "-complexes
29 rganocuprate Reactions: Atom Economy
30 rganocuprate Reactions: Atom Economy H H H
31 Mixed cuprates: Non transferable ligands (dummy ligands) Corey et al, J. rg. Chem. 1978, 17, Nilsson et al, J. rganometallic Chem., 1986, 334, Posner et al, J. Am. Chem. oc. 1973, 95, Bertz et al, J. Am. Chem. oc. 1996,
32 Mixed organocuprate preparation route 1: I R R R -78 o C -78 o C RR olid oluble R = H 2 CD C 3 i CD3 CD 3 Ph P Ph
33
34
35 ynthesis of: (CD 3 ) 3 ich 2
36
37 Mixed organocuprate preparation route 2: R R -78 o C RR R = CN, Ph
38 CD 3 D 3 C CH MgCl CN -78 o C D 3 C H C CNMgCl D 3 C
39 ummary of cyano based mixed cuprates CN RM -78 o C RCNM R = H 3 C H 3 C H 2 C MgCl H CD 3 D3 C C MgCl H 3 C H 2 C CH2 H 2 C
40
41 Conjugate addition pathway with mixed cuprates = CH 3 = dummy lignad TMCN xidative Addition TM TM NC NC! -CN( ) TM
42 Conjugate addition pathway with mixed cuprates = CH 3 = dummy lignad TMCN xidative Addition TM TM NC NC! -CN( ) TM
43
44
45 H 3 C Chalcone -100 C Ph CH3 Ph
46 CH 2 i(cd 3 ) 3 /I H 2 C i(cd 3) 3 i(cd 3 ) 3 CH2 CH 3
47 CH 2 i(cd 3 ) 3 /I H 2 C i(cd 3) 3 i(cd 3 ) 3 CH2 CH 3 i(cd 3 ) 3 CH3 (D 3 C) 3 i C H 3 CH 3 Yamanaka, M., Nakamura, E., J Am. Chem. oc. 2005, 127,
48 Characterization: Trans effect
49 Ph + Chalcone NE
50 H 3 C C C MVK
51 H 3 C C C
52 Asymmetric Induction with mixed organocuprates gle, C. A.; Human, J. B. Tetrahedron: Asymmetry 2003, 14,
53 Ph Ar!I Ph Ar CH3 Ph Ar CH3 Ph CH 3 CH3 Ph Ph Ph Ph N = Ar
54 Possible tathesis Pathways Equilibration through the mixed cuprates Reaction of a mixed cuprate with a "-complex
55 1 st Possible tathesis Pathway
56 2 nd Possible tathesis Pathway
57 Proposed product formation pathways Ph Ph (Ph) 2 + Ph + CH3 -Ph CH 3 Ph CH 3 + CH3 CH 3 (Ph) 2
58 Examples of Michael Acceptors Used in tudy
59 Conclusions (III) intermediates have been observed in the conjugate addition reactions, alkylation reactions and allylation reactions. Tetraalkylcuprates react with electrophilic reagents and slowly with weak acids such as methanol at low temperatures. The conjugate addition reaction pathway was originally thought to be straightforward nly one of two possible "-complexes was formed, and the methyl was poised for transfer ome of the mixed cuprate "-complexes readily underwent metathesis to the corresponding homocuprate "- complexes
60 ACKNWLEDGEMENT ACKNWLEDGEMENT Dr. Craig gle, Dr. Mike Murphy and Dr. teve Bertz teven Cope, Richard Hardin, Josh Richter NF # & RACheL
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