Supporting Information

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1 Supporting Information Ruthenium-Catalyzed Oxidative Annulation and Hydroarylation of Chromene-3- carboxamides with Alkynes via Double C-H Functionalization R. N. Prasad Tulichala, Mallepalli Shankar and K. C. Kumara Swamy* School of Chemistry, University of Hyderabad, Hyderabad , Telangana, India ORTEPs for compounds 5aj, 5ba, 6af and 6ba (Figures S1- S4) 2 Plausible pathway for the formation of 5aa, Scheme S1, Scheme S2, and Figure S5 S2-S3 S4-S6 3 Copies of 1 H/ 13 C NMR spectra for precursors 3a-d and 3f S7-S11 4 Copies of 1 H/ 13 C NMR spectra for compounds 5aa-5al and 5ba-5fa 5 Copies of 1 H/ 13 C NMR spectra for compounds 6ab-6af, 6ah, 6ba, 6al (along with 1 H NMR spectra of different fractions from column chromatography) 6 Copies of 19 F NMR spectra for compounds 5ad, 5ae, 6ad and 6ae S12-S28 S29-S37 S38-S41 S1

2 (1) ORTEPs for compounds 5aj, 5ba, 6af and 6ba Figure S1. ORTEP (ellipsoid contour probability 50%) of compound 5aj. Selected bond lengths [Å] with esd s in parentheses: N(1)-C(13) 1.390(2), C(10)-C(13) 1.366(2), C(10)-C(9) 1.439(2), C(9)-C(8) 1.369(2), C(8)-C(27) 1.433(2), N(1)-C(27) 1.397(2). Hydrogen atoms are omitted for clarity. CCDC No Figure S2. ORTEP (ellipsoid contour probability 50%) of compound 5ba. Selected bond lengths [Å] with esd s in parentheses: N(1)-C(18) 1.382(3), C(11)-C(18) 1.357(3), C(7)-C(11) 1.442(3), C(7)-C(8) 1.367(3), C(8)-C(10) 1.416(3), N(1)-C(10) 1.403(3). Hydrogen atoms are omitted for clarity. CCDC No S2

3 Figure S3. ORTEP (ellipsoid contour probability 50%) of compound 6af. Selected bond lengths [Å] with esds in parentheses: N(1)-C(19) 1.391(2), C(19)-C(10) 1.376(3), C(8)-C(9) 1.363(3), C(10)-C(9) 1.442(3), C(34)-C(35) 1.500(2), C(35)-C(36) 1.340(3). H-atoms are not shown for clarity. CCDC No Figure S4. ORTEP (ellipsoid contour probability 50%) of compound 6ba. Selected bond lengths [Å] with esds in parentheses: N(1)-C(11) 1.385(3), C(11)-C(12) 1.373(3), C(12)-C(1) 1.437(3), C(1)-C(9) 1.361(3), C(9)-C(10) 1.428(3), N(1)-C(10) 1.398(3). H-atoms are not shown for clarity. CCDC No S3

4 Plausible pathway for the formation of benzopyran-fused 2-pyridone 5aa A plausible reaction pathway based on literature reports 1 to account for the annulation reaction is proposed in Scheme S1. Initially, [RuCl 2 (p-cymene)] 2 undergoes ligand exchange with Cu(OAc) 2 to give the mono-acetate [RuCl(OAc)(p-cymene)]. This proposal is based on previous reports from our laboratory. 2 The active cationic ruthenium species I is generated by the ligand exchange reaction between [RuCl(OAc)(p-cymene)] and AgNTf 2. Here the role of AgNTf 2 is to remove the Cl ligand from the mono-acetate [RuCl(OAc)(p-cymene)] complex providing a cationic ruthenium species I. Coordination of the nitrogen of the amide in chromene- 3-carboxamide 3a to ruthenium species followed by subsequent N-H bond cleavage and ortho metalation at C(4)-H of the chromene moiety affords the five-membered ruthenacycle II after elimination of AcOH. Reaction of complex II with D 2 O, in principle, should give rise to deuteration at C4-H, but for this is perhaps complicated by the presence of exchangeable NHR proton as well as the presence of coordinated water in Cu(OAc) 2.H 2 O. Use of Cu(OAc) 2.D 2 O prepared by exchanging the coordinated water with D 2 O did lead to significant incorporation of C4-D (see experimental section), but there is evidence [HRMS] to suggest that a second deuterium also entered in the compound 3a (cf. Scheme S2 and Figure S5). Complex II subsequently undergoes migratory insertion with alkyne 4a into the Ru-C bond leading to the seven-membered ruthenium intermediate III. Finally, intermediate III undergoes reductive elimination in the presence of Cu(OAc) 2 providing the benzopyran fused 2-pyridone 5aa and regenerating the active ruthenium(ii) catalyst. In the case of the unsymmetrical alkyne 4j, the regioselective formation of the benzopyran fused 2-pyridone 5aj is explained by intramolecular coordination of the phenyl group to the Ru metal that could stabilize intermediate III. 3 Hence the phenyl group always tends to stay close to the Ru metal in intermediate III. S4

5 Scheme S1. Plausible Pathway for the Formation of Benzopyran-fused 2-Pyridone 5aa Scheme S2. H/D exchange reaction in CD 3 OD S5

6 ppm Figure S5. 1 H-NMR spectrum of the product after treating 3a with Ru catalyst, Cu(OAc) 2.D 2 O, AgNTf 2 in CD 3 OD showing partially deuterated compound 3a- D in the region Note the significant reduced intensity of the singlet at 7.08; there is also significant reduction (from two protons to one proton) in the intensity of the aromatic multiplet at (a) Ackermann, L.; Lygin, A. V.; Hofmann, N. Org. Lett. 2011, 13, (b) Li, B.; Feng, H.; Xu, S.; Wang, B. Chem. Eur. J. 2011, 17, (c) Kaishap, P. P.; Sarma, B.; Gogoi, S. Chem. Commun. 2016, 52, 9809, and references cited therein. (d) Fabre, I.; Wolff, N. V.; Duc, G. L.; Flegeau, E. F.; Dixneuf, P. H.; Jutand, A. Chem. Eur. J. 2013, 19, (e) Warratz, S.; Kornhaaß, C.; Cajaraville, A.; Niepötter, B.; Stalke, D.; Ackermann, L. Angew. Chem. Int. Ed. 2015, 54, 5513 and references cited therein. (f) Manoharan, R.; Jeganmohan, M. Chem. Commun. 2015, 51, (g) Gensch, T.; Hopkinson, M. N.; Glorius, F.; Wencel- Delord, J. Chem. Soc. Rev. 2016, 45, 2900 and references cited therein. 2. (a) Allu, S.; Kumara Swamy, K. C. J. Org. Chem. 2014, 79, (b) Allu, S.; Kumara Swamy, K. C. Adv. Synth. Catal. 2015, 357, (a) Chinnagolla, R. K.; Pimparkar, S.; Jeganmohan, M. Chem. Commun. 2013, 49, (b) Padala, K.; Jeganmohan, M. Chem. Commun. 2014, 50, S6

7 (3) Copies of 1 H/ 13 C NMR spectra for starting precursors Figure S6. 1 H-NMR spectrum of compound 3a Figure S7. 13 C-NMR spectrum of compound 3a S7

8 Figure S8. 1 H-NMR spectrum of compound 3b Figure S9. 13 C-NMR spectrum of compound 3b S8

9 Figure S10. 1 H-NMR spectrum of compound 3c Figure S C-NMR spectrum of compound 3c S9

10 Figure S12. 1 H-NMR spectrum of compound 3d Figure S C-NMR spectrum of compound 3d S10

11 Figure S14. 1 H-NMR spectrum of compound 3f Figure S C-NMR spectrum of compound 3f S11

12 (4) Copies of 1 H/ 13 C NMR spectra for compounds 5aa-5al and 5ba-5fa Figure S16. 1 H-NMR spectrum of compound 5aa Figure S C-NMR spectrum of compound 5aa S12

13 Figure S18. 1 H NMR spectrum of compound 5ab Figure S C-NMR spectrum of compound 5ab S13

14 Figure S20. 1 H-NMR spectrum of compound 5ac Figure S C-NMR spectrum of compound 5ac S14

15 Figure S22. 1 H-NMR spectrum of compound 5ad Figure S C-NMR spectrum of compound 5ad S15

16 Figure S24. 1 H NMR spectrum of compound 5ae Figure S C-NMR spectrum of compound 5ae S16

17 Figure S26. 1 H-NMR spectrum of compound 5af Figure S C-NMR spectrum of compound 5af S17

18 Figure S28. 1 H NMR spectrum of compound 5ag Figure S C-NMR spectrum of compound 5ag S18

19 Figure S30. 1 H-NMR spectrum of compound 5ah Figure S C-NMR spectrum of compound 5ah S19

20 Figure S32. 1 H-NMR spectrum of compound 5ai Figure S C-NMR spectrum of compound 5ai S20

21 Figure S34. 1 H-NMR spectrum of compound 5aj Figure S C-NMR spectrum of compound 5aj S21

22 Figure S36. 1 H-NMR spectrum of compound 5ak Figure S C-NMR spectrum of compound 5ak S22

23 Figure S38. 1 H-NMR spectrum of compound 5al Figure S C-NMR spectrum of compound 5al (1:1 isomeric mixture) S23

24 Figure S40. 1 H-NMR spectrum of compound 5ba Figure S C-NMR spectrum of compound 5ba S24

25 Figure S42. 1 H-NMR spectrum of compound 5ca Figure S C-NMR spectrum of compound 5ca S25

26 Figure S44. 1 H-NMR spectrum of compound 5da Figure S C-NMR spectrum of compound 5da S26

27 Figure S46. 1 H-NMR spectrum of compound 5ea Figure S C-NMR spectrum of compound 5ea S27

28 Figure S48. 1 H-NMR spectrum of compound 5fa Figure S C-NMR spectrum of compound 5fa S28

29 (5) Copies of 1 H/ 13 C NMR spectra for compounds 6ab-6af, 6ah, and 6ba Figure S50. 1 H-NMR spectrum of compound 6ab Figure S C-NMR spectrum of compound 6ab S29

30 Figure S52. 1 H-NMR spectrum of compound 6ac Figure S C-NMR spectrum of compound 6ac S30

31 Figure S54. 1 H-NMR spectrum of compound 6ad Figure S C-NMR spectrum of compound 6ad S31

32 Figure S56. 1 H-NMR spectrum of compound 6ae Figure S C-NMR spectrum of compound 6ae S32

33 Figure S58. 1 H-NMR spectrum of compound 6af Figure S C-NMR spectrum of compound 6af S33

34 Figure S60. 1 H-NMR spectrum of compound 6ah Figure S C-NMR spectrum of compound 6ah S34

35 Figure S62. 1 H-NMR spectrum of compound 6ba Figure S C-NMR spectrum of compound 6ba S35

36 ppm ppm Figure S64. 1 H NMR spectrum of 6al (fraction d from in Figure 66; see text for details) ppm ppm Figure C NMR spectrum of 6al (fraction d from in Figure 66; see text for details) S36

37 (e) ppm (d) ppm (c) ppm (b) ppm (a) ppm Figure S66. 1 H NMR spectra ( ): Trace (a) is the mixture containing 6al and 5al in the reaction of 3a with two equivalents of 4l. Traces (b)-(e) are sequential fractions from column chromatography. S37

38 (6) Copies of 19 F NMR spectra for compounds 5ad, 5ae, 6ad and 6ae Figure S F-NMR spectrum of compound 5ad S38

39 Figure S F-NMR spectrum of compound 5ae S39

40 Figure S F-NMR spectrum of compound 6ad S40

41 Figure S F-NMR spectrum of compound 6ae S41