Supporting Information. Gold Catalyzed β Regioselective Formal [3+2] Cycloaddition of. Ynamides with Pyrido[1,2 b]indazoles: Reaction Development

Transcription

1 Supporting Information Gold Catalyzed β Regioselective Formal [+] Cycloaddition of Ynamides with Pyrido[, b]indazoles: Reaction Development and Mechanistic Insights Yinghua Yu, a Gui Chen, a Lei Zhu, a Yun Liao, a,b Yufeng Wu, a,b Xueliang Huang* a a Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou,, P. R. China b College of Chemistry, Fuzhou University, Fuzhou, Fujian, P. R. China huangxl@fjirsm.ac.cn Table of Contents Kinetic Studies... S H, C and P NMR spectra for JohnphosAu(a)SbF... S H, C and P NMR spectra for JohnphosAu(a)SbF... S H and C NMR spectra for the prepared substrates... S H and C NMR spectra for the prepared products... S S

2 Kinetic Studies A mixture of ynamides, pyrido[,-b]indazoles and JohnphosAu(MeCN)SbF in ml CDCl was stirred under argon at desired temperature. μl of the mixture was sampled by a syringe at desired time. The concentration of is obtained by H NMR Spectroscopy based on the internal standard (dibromomethane). All reaction was monitored to ~ % yield of. Initial rates were obtained by linear fit of the concentration-time plot. A plot of ln(initial rate) vs. ln([au]), ln([a]) or In([a]) showed that the reaction was first-order in JohnphosAu(MeCN)SbF (Figure S) and zero-order in both a and a (Figure S and S, equation ). Effect of temperature. The effect of temperature on initial rate for the reaction between a and a catalyzed by JohnphosAu(MeCN)SbF was studied from to K (Figure S). The activation parameters were obtained from the plot of ln(initial rate/t) vs /T according to Eyring equation. ΔH and ΔS were found to be. kcal mol - and. cal mol - K -, respectively. The negative S value suggests that atransition state involving catalyst, a and a might be generated. S

3 Effects of substituent X in on the reaction: The relative rate was calculated by k X /k H. k represents the initial rate for the reaction between a and catalyzed by JohnphosAu(MeCN)SbF in CDCl at o C (Figure S). Scheme S. Effects of substituent X in on the reaction. Hammett Correlation. The electronic effects of substituent X at the para-position of the phenyl ring in ynamides on the rate constants of this reaction have been correlated by Hammette quation, log(k X /k H ) = ρσ. The plot of log(k X /k H ) against σ shows a linear relationship (Figure S), with the slope ρ = -.. The large negative ρ value suggests that the transition state of the reaction is polarized with positive charge at the reaction center. Scheme S. Effects of substituent X in on the reaction. Kinetic isotope effect experiments. As C-H functionalization of the aromatic ring was involved in current transformation. To identify whether the cleavage of the C-H at the ortho-position of pyrido[,-b]indazoles a is the rate-determined step, kinetic isotope effect of parallel experiments were carried out (Scheme S and Figure ). However, no significant kinetic isotope effect (k H /k D =.) was observed, suggesting that C-H bond cleavage was not involved in the rate-determined step. S

4 Scheme S. Kinetic isotope effect experiments Figure S. The P NMR spectroscopy of (A) mixture of μmol JohnposAu(MeCN)SbF and μmol a, (B) mixture of μmol JohnposAu(MeCN)SbF, μmol a and μmol a in. ml CDCl. S

5 . AuL(a) +.. AuL(a) + m/z. AuL(H O) +. AuL +. AuL(MeCN) +. AuL(a)(a) + m/z Figure S. High resolution electrospray ionization mass spectrometry (ESI-HRMS) of the mixture of mmol of JohnposAu(MeCN)SbF, mmol of a and mmol of a in ml MeCN. For clarity, data reported herein were obtained without calibration by addition of internal standard. In a paralleled experiment using sodium formate as internal standard, the exact m/z of AuL(a) +, AuL(a) +, AuL(a)(a) + are found to be.,. and. respectively after calibration. [aa] / M [Au]. mm (y =.x +., R =.). mm (y =.x +., R =.). mm (y =.x +., R =.). mm (y =.x +., R =.). mm (y =.x +., R =.) Time / min In(initial rate) y =.x -., R = In[Au] Figure S. (Left) plots of concentration of aa vs time for the reaction between a and acatalyzed by JohnphosAu(MeCN)SbF in CDCl at o C. [Au] =.. mm, [a] =. M, [a] =. M. (Right) Plot of ln(initial rate) vs ln([au]). y =.x., R =.. The slope of the line is approximately, indicating that the rate for the reaction between a and a catalyzed by JohnphosAu(MeCN)SbF is first-order in JohnphosAu(MeCN)SbF. S

6 [aa] / M [a]. M (y =.x +., R =.). M (y =.x +., R =.). M (y =.x +., R =.). M (y =.x +., R =.). M (y =.x +., R =.). M (y =.x +., R =.) In(Initial rate) Time / min y =.x -., R = In[a] Figure S. (Left) plots of concentration of aa vs time for the reaction between a and acatalyzed by JohnphosAu(MeCN)SbF in CDCl at o C. [Au] =. mm, [a] =.. M, [a] =. M. (Right) Plot of ln(initial rate) vs ln([a]). y =.x., R =.. The slope of the line is approximately, indicating that the rate for the reaction between a and acatalyzed by JohnphosAu(MeCN)SbF is zero-order in a. [aa] / M [a].. M (y =.x +., R =.). M (y =.x +., R =.).. M (y =.x +., R =.).. M (y =.x +., R =.). M (y =. x +., R =.)..... Time / min In(initial rate) y = -.x -., R = In[a] Figure S. (Left) plots of concentration of aa vs time for the reaction between a and acatalyzed by JohnphosAu(MeCN)SbF in CDCl at o C. [Au] =. mm, [a] =. M, [a] =.. M. (Right) Plot of ln(initial rate) vs ln([a]). y =.x., R =.. The slope of the line is approximately, indicating that the rate for the reaction between a and a catalyzed by JohnphosAu(MeCN)SbF is zero-order in a. S

7 [aa] / M o C (y =.x +., R =.) o C (y =.x +., R =.) o C (y =.x +., R =.) o C (y =.x +., R =.) o C (y =.x +., R =.). Time / min In(initial rate/t) y = -.x +., R = /T (K - ) Figure S. (Left) plots of concentration of aa vs time for the reaction between a and a catalyzed by JohnphosAu(MeCN)SbF in CDCl. [Au] =. mm, [a] =. M, [a] =. M. (Right) Plot of ln(initial rate/t) vs /T, slope = -., y-intercept =., r =.. [] / M R = H (y =.x +., R =.) R = Me (y =.x +., R =.) R = Cl (y =.x +., R =.) R = Br (y =.x +., R =.) R = F (y =.x +., R =.) R = MeO (y =. x +., R =.) Time / min Log(k X /k H ) MeO Me H F Cl y = -.x +., R =. Br Figure S. (Left) plot of concentration of vs time for the reaction between and a catalyzed by JohnphosAu(MeCN)SbF in CDCl at o C. [Au] =. mm, [] =. M, [a] =. M. (Right) Hammett plot of log(k X /k H ) vs σ, slope = -., y-intercept =., r =.. S

8 .... X = H (y =.x +., R =.) X = CO Me (y =.x +., R =.) X = F (y =.x +., R =.) X = Me (y =.x +., R =.) X = OMe (y =. x +., R =.) X = Br (y =. x +., R =.) [] / M..... Time / min Figure S. Plot of concentration of vs time for the reaction between a and catalyzed by JohnphosAu(MeCN)SbF in CDCl at o C. [Au] =. mm, [a] =. M, [] =. M.. a-h (y =.x +., R =.) a-d (y =.x +., R =.). [aa] / M... Time / min Figure. Kinetic profiles for the gold-catalyzed annultion of ynamides a with pyrido[,-b]indazoles a-h (black) and a-d (red). Yields were obtained by H MNR using dibromomethane as internal standard. Standard reaction conditions: [a] =. M, [a] =. M, [Au] = mm in. ml CDCl under argon at o C. S

9 Figure S. X-ray structure of aa. Hydrogen atoms have been omitted for clarity. The thermal ellipsoid was drawn at the % probability level. CCDC. Bond precision: C-C =. A Wavelength=. Cell: a=.() b=.() c=.() alpha= beta=.() gamma= Temperature: K Calculated Reported Volume.().() Space group P /c P()/c Hall group -P ybc Moiety formula C H N O Sum formula C H N O C H N O Mr.. Dx,g cm-.. Z Mu (mm-).. F.. F. h,k,lmax,,,, Nref Tmin,Tmax.. Tmin. Correction method= Not given Data completeness=. Theta(max)=. R(reflections)=.( ) wr(reflections)=.( ) S =. Npar= S

10 Figure S. X-ray structure of ah. Hydrogen atoms have been omitted for clarity. The thermal ellipsoid was drawn at the % probability level. CCDC. Bond precision: C-C =. A Wavelength=. Cell: a=.() b=.() c=.() alpha= beta=.() gamma= Temperature: K Calculated Reported Volume.().() Space group P /n P()/n Hall group -P yn Moiety formula C H N O Sum formula C H N O C H N O Mr.. Dx,g cm-.. Z Mu (mm-).. F.. F. h,k,lmax,,,, Nref Tmin,Tmax.. Tmin. Correction method= Not given Data completeness=. Theta(max)=. R(reflections)=.( ) wr(reflections)=.( ) S =. Npar= S

11 Figure S. X-ray structure of ca. Hydrogen atoms have been omitted for clarity. The thermal ellipsoid was drawn at the % probability level. CCDC. Bond precision: C-C =. A Wavelength=. Cell: a=.() b=.() c=.() alpha= beta=.() gamma= Temperature: K Calculated Reported Volume.().() Space group P /c P/c Hall group -P ybc Moiety formula C H N O Sum formula C H N O C H N O Mr.. Dx,g cm-.. Z Mu (mm-).. F.. F. h,k,lmax,,,, Nref Tmin,Tmax.. Tmin. Correction method= Not given Data completeness=. Theta(max)=. R(reflections)=.( ) wr(reflections)=.( ) S =. Npar= S

12 Figure S. X-ray structure of JohnphosAu(a)SbF. Hydrogen atoms have been omitted for clarity. The thermal ellipsoid was drawn at the % probability level. CCDC. Bond precision: C-C =. A Wavelength=. Cell: a=.() b=.() c=.() alpha= beta=.() gamma= Temperature: K Calculated Reported Volume.().() Space group P /c P /c Hall group -P ybc -P ybc Moiety formula C H Au N O P, F Sb, C H Cl Sum formula C H Au Cl F N O P Sb C H Au Cl F N O P Sb Mr.. Dx,g cm-.. Z Mu (mm-).. F.. F. h,k,lmax,,,, Nref Tmin,Tmax.,..,. Tmin. Correction method= # Reported T Limits: Tmin=. Tmax=. AbsCorr = MULTI-SCAN Data completeness=. Theta(max)=. R(reflections)=.( ) wr(reflections)=.( ) S =. Npar= S

13 Figure S. X-ray structure of JohnphosAu(a)SbF. Hydrogen atoms have been omitted for clarity. The thermal ellipsoid was drawn at the % probability level. CCDC. Bond precision: C-C =. A Wavelength=. Cell: a=.() b=.() c=.() alpha=.() beta=.() gamma=.() Temperature: K Calculated Reported Volume.().() Space group P - P- Hall group -P Moiety formula C H Au N P, F Sb Sum formula C H Au F N P Sb C H Au F N P Sb Mr.. Dx,g cm-.. Z Mu (mm-).. F.. F. h,k,lmax,,,, Nref Tmin,Tmax.,..,. Tmin. Correction method= # Reported T Limits: Tmin=. Tmax=. AbsCorr = MULTI-SCAN Data completeness=. Theta(max)=. R(reflections)=.( ) wr(reflections)=.( ) S =. Npar= S

14 H, C and P NMR spectra for JohnphosAu(a)SbF S

15 S

16 S H, C and P NMR spectra for JohnphosAu(a)SbF yyh yyh yyh yyh yyh

17 yyh S

18 H and C NMR spectra for the prepared substrates yyh yyh S

19 S yyh yyh

20 S cg cg

21 S cg cg

22 S cg cg

23 S yyh-b yyh-b

24 S yyh yyh

25 S cg cg

26 S yyh-b yyh-b

27 S yyh-a yyh-a

28 S cg cg

29 S cg cg

30 S cg cg

31 S yyh-a yyh-a

32 S cg cg

33 S cg cg

34 S cg cg

35 S H and C NMR spectra for the prepared products yyh yyh yyh yyh

36 S yyh yyh

37 S yyh yyh

38 S yyh yyh

39 S yyh yyh yyh

40 yyh S

41 S yyh yyh

42 S yyh yyh

43 S yyh yyh

44 S yyh yyh

45 S yyh yyh

46 S yyh yyh

47 S yyh yyh

48 S yyh yyh yyh yyh

49 S cgmecn cg

50 cg-f S

51 S cg cg

52 S cg cg

53 S yyh yyh

54 S yyh yyh

55 S cg cg

56 S yyh-b yyh-b yyh-b yyh-b yyh-b

57 S yyh yyh yyh

58 S cg cg cg

59 S cg cg cg cg

60 S cg cg cg cg

61 S yyh yyh yyh yyh

62 S cg cg cg cg

63 S cg cg cg cg

64 S cg cg cg cg

65 H, B, C and F NMR spectra for, difluoro ( oxooxazolidin yl) phenyl H pyrido[',':,] [,,]diazaborinino[,, hi]indol ium uide S

66 S