Supporting Information

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1 S1 Supporting Information to Transfer hydrogenation of nitriles, olefins, and N-heterocycles catalyzed by an NHC-supported half-sandwich complex of ruthenium Van Hung Mai and Georgii Nikonov* Chemistry Department, Brock University, Niagara Region, 1812 Sir Isaac Brock Way, St. Catharines, ON L2S 3A1, Canada. Tel.: +1 (95) , ext 335, Fax: +1 (95) Corresponding Author * Georgii Nikonov, gnikonov@brocku.ca Table of Contents 1 Catalytic studies S2 2 Kinetic studies..s5 3 NMR Spectra.. S13

2 S2 1 Catalytic studies Table S1. Comparison of catalytic activity of complexes 2-4 in the TH of acetophenone and benzonitrile Entry Cat a,b Substrate Product Yield (%) Time h2m h2m h 4 4a 37 8h h15m h13m h 8 4a 34 8h a.5 mol % cat,.5 mol % of KO t Bu in isopropanol at 8ºC for acetophenone. b.5 mol % cat, 1.5 mol % of KO t Bu in isopropanol at 7ºC for benzonitrile. Table S2. Optimization of the amount of base (KOBu t ) in the TH of benzonitrile catalyzed by complex 3 Entry Substrates Products Yield a (%) Time Base : Catal h h43m h36m h5m h54m 4

3 S h29m h25m h15m h5m 2 a.5 mol % 3 and variable amount of KO t Bu in isopropanol at 7ºC. Yields determined by NMR. Entr y Table S3. Attempted transfer hydrogenation of esters catalyzed by [Cp(IPr)Ru(pyr) 2 ][PF 6 ] (3) a Substrate Product Conversion (%) b Time Note c 1 ethyl benzoate PhCO 2 CH(CH 3 ) 2 5 5m TE ethyl 4- acetylbenzoate ethyl 4- aminobenzoate ethyl(dimethylamin o)-benzoate methyl 3- cyanobenzoate phenyl 4- methoxybenzoate 7 phenyl benzoate methylphenyl benzoate ethyl 4- nitrobenzoate 4- {CH 3 CH(OH)}C 6 H 6 CO 2 CH(C H 3 ) 2 99 (16) 5m TE+T H 4-H 2 NC 6 H 4 CO 2 CH(CH 3 ) 2 ) 99 1m TE 4-(CH 3 ) 2 NC 6 H 4 CO 2 C(CH 3 ) m TE 3-CH 3 O 2 CC 6 H 4 CH 2 N=C(CH 3 ) h35m TE 4-CH 3 OC 6 H 4 CO 2 C(CH 3 ) m TE PhCO 2 CH(CH 3 ) 2, and PhCH 2 OH 4-CH 3 C 6 H 4 CO 2 CH(CH 3 ) CH 3 C 6 H 4 CH 2 OH 4 68 (11) 9h 11h3 m 4-H 2 NC 6 H 4 CO 2 CH(CH 3 ) 2 99(<5) 5m 1 vinyl benzoate PhCO 2 CH(CH 3 ) 2 < chlorobenzoyl benzoate 11h3 m TE TE+T H TE+T H 4-ClC 6 H 4 CO 2 C(CH 3 ) 2 2 4h TE TE

4 S4 12 phenyl acetate PhCO 2 C(CH 3 ) 2 +PhCH 2 OH 5 (1) 2h ethyl triflouroacetate phenyl triflouroacetate CF 3 CH 2 OH, CH 3 CH 2 OH 86 (8) 1h45m PhOH and CF 3 CH 2 OH 68 (<5) 2h4m TE+T H TE+T H TE+T H 15 dimethyl phthalate NR - 2h TE a 1 mol % 3, 3 mol % of KO t Bu in isopropanol at 7ºC; b Conversion to the transferhydrogenated (TH) products in parentheses; conversions determined by NMR.; c TH=transfer-hydrogenation, TE=trans-esterification.

5 S5 2 Kinetic studies on transfer hydrogenation of p-methoxybenzonitrile with isopropanol Kinetic sample preparation Table S4. Sample preparation for variation of isopropanol Sample number IPA ratios to substrate IPA amount (µl) Catalyst stock solution (µl) Substrate stock (µl) KOtBu stock in PhCl (µl) Adding more PhCl fresh (µl) Total (µl)

6 Ln(Xt/Xo) Ln(Xt/Xo) S y =.99x -.21 R² = time, sec Figure S1. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (1 equivs of IPA) y =.77x R² =.991 time, sec Figure S2. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (15 equivs of IPA).

7 Ln(Xt/Xo) Ln(Xt/Xo) S y =.857x R² = time, sec Figure S3. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (2 equivs of IPA) y =.995x R² = time,sec Figure S4. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (25 equivs of IPA).

8 Ln(Xt/Xo) Ln(Xt/Xo) S y =.1111x R² = time, sec Figure S5. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (3 equivs of IPA) y =.94x R² = time, sec Figure S6. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (35 equivs of IPA).

9 Ln(Xt/Xo) S y =.958x -.86 R² = time, sec Figure S7. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions (4 equivs of IPA). Table S5. Sample preparation for variation of base Sample number Base ratio B:C Catalyst stock solution (µl) Substrate stock (µl) KOBu t stock in IPA (µl) Fresh IPA add more (µl) PhCl added more (µl) Total (µl)

10 Ln(Xt/Xo) Ln(Xt/Xo) S y =.114x R² = Time (s) Figure S8. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions without added KOBu t y =.1295x R² = Time (s) Figure S9. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions with.5 equiv of KOBu t.

11 Ln(Xt/Xo) Ln(Xt/Xo) S y =.1231x R² =.9926 Time (s) Figure S1. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions with 1 equiv of KOBu t y =.299x -.44 R² =.9922 Time (s) Figure S11. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions with 2 equiv of KOBu t.

12 Ln(Xt/Xo) S y =.21x +.8 R² = Figure S12. Plot ln([mephcn] t /[MePhCNe] ) versus time under pseudo-first order conditions with 3 equiv of KOBu t..14 K eff vs base K eff y = -.498x R² = equivs of tbuok Figure S13. The dependence of reaction rate on the amount of KOBu t.

13 S13 3 Selected NMR Spectra Isolated ammonium salts and amines CH 3 (CH 2 ) 5 NH 3 Cl Figure S14. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of CH 3 (CH 2 ) 5 NH 3 Cl

14 S14 CH 3 (CH 2 ) 3 NH 2 Figure S15. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra CH 3 (CH 2 ) 4 NH 2

15 S15 4-(CH 3 O)C 6 H 4 CH 2 NH 3 Cl Figure S16. 1 H (4 MHz, D 2 O) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of 4- (CH 3 O)C 6 H 4 CH 2 NH 3 Cl

16 S16 4-(NH 2 )C 6 H 4 CH 2 NH 3 Cl Figure S17. 1 H (4 MHz, D 2 O) and 13 C{ 1 H}(1.6 MHz, D 2 O) NMR spectra of 4- (NH 2 )C 6 H 4 CH 2 NH 3 Cl

17 S17 C 6 H 5 CH 2 NH 3 Cl Figure S18. 1 H (4 MHz, D 2 O) and 13 C{ 1 H}(1.6 MHz, D 2 O) NMR spectra of C 6 H 5 CH 2 NH 3 Cl

18 S18 1,2,3,4-tetrahydroquinoline Figure S19. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of 1,2,3,4-tetrahydroquinoline

19 S19 Hydrogenated conjugated olefins Ethylbutyrate Figure S2. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of ethylbutyrate

20 S2 Isopropyl isobutyrate Figure S21. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of isopropyl isobutyrate

21 S21 Propionamide Figure S22. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of propionamide

22 S22 Isobutyramide Figure S23. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of isobutyramide

23 S23 Ethyl isobutyrate Figure S24. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of ethyl isobutyrate

24 S24 Methyl propionate Figure S25. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of methyl propionate

25 S25 Ethyl propionate Figure S26. 1 H (4 MHz, CDCl 3 ) and 13 C{ 1 H}(1.6 MHz, CDCl 3 ) NMR spectra of ethyl propionate

Enantioselective Organocatalytic Michael Addition of Malonate Esters to Nitro Olefins Using Bifunctional Cinchonine Derivatives

Enantioselective Organocatalytic Michael Addition of Malonate Esters to Nitro Olefins Using Bifunctional Cinchonine Derivatives Enantioselective rganocatalytic Michael Addition of Malonate Esters to itro lefins Using Bifunctional Cinchonine Derivatives Jinxing Ye, Darren J. Dixon * and Peter S. Hynes School of Chemistry, University