Electronic Supplementary Information - The … Supplementary Information Towards a General Ruthenium-Catalyzed Hydrogenation of Secondary and Tertiary Amides to Amines Jose R. Cabrero-Antonino,a
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Electronic Supplementary Information
Towards a General Ruthenium-Catalyzed Hydrogenation of Secondary and Tertiary Amides to Amines
Jose R. Cabrero-Antonino,a Elisabetta Alberico,a,b Kathrin Junge,a Henrik Jungea and Matthias Bellera*
a Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany; Fax: (+49) 381-1281-5000b Istituto di Chimica Biomolecolare, Consiglio Nazionale delle Ricerche, Tr. La Crucca 3, 07100 Sassari, Italy. *E-mail: [email protected]
1. GENERAL INFORMATION
2. EXPERIMENTAL PROCEDURES
3. ADDITIONAL TABLES
Table S1. Hydrogenation of benzanilide (1) with the [Ru/Triphos/Hf(OTf)4] system: Influence of the hydrogen
pressure and temperature Table S2. Hydrogenation of benzanilide (1) with the [Ru/Triphos/additive] system: screening of various Lewis
and Brönsted acids as co-catalyst
Table S3. Hydrogenation of benzanilide (1) with the [Ru/Triphos/Yb(OTf)3.H2O] system: screening of different
ruthenium precursors Table S4. Hydrogenation of benzanilide (1) with the [Ru/L/Yb(OTf)3.H2O] system: screening of different
phosphorus ligands
Table S5. Hydrogenation of benzanilide (1) with the [Ru/Triphos/Yb(OTf)3.H2O] system: Influence of the
solvent
Table S6. Hydrogenation of benzanilide (1) with the [Ru/Triphos/Yb(OTf)3.H2O] system: yield/time profile at 5
[a] Standard reaction conditions: benzanilide 1 (100.6 mg, 0.5 mmol), Ru catalyst (2 mol%), triphos (4 mol%), Hf(OTf)4 (4 mol%), THF (2 mL) and H2 (15-50 bar) at 130-170 °C for 15 h. [b] Conversion of 1 and yields of 2, 3, and 4 were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-15%) were produced following acid promoted ring-opening of THF.
Table S2. Hydrogenation of benzanilide (1) with [Ru/Triphos/additive] system: screening of various Lewis and
[a] Standard reaction conditions: benzanilide 1 (100.6 mg, 0.5 mmol), Ru(acac)3 (2 mol%), triphos (4 mol%), additive (2-16 mol%), THF (2 mL) and H2 (15 bar) at 150 °C during 15 h. [b] Conversion of 1 and yields of 2, 3, and 4 were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-15%) were produced following acid promoted ring-opening of THF.
Table S3. Hydrogenation of benzanilide (1) with [Ru/Triphos/Yb(OTf)3.H2O] system: screening of different
[a] Standard reaction conditions: benzanilide 1 (100.6 mg, 0.5 mmol), Ru catalyst (2 mol%), triphos (4 mol%), Yb(OTf)3.H2O (4 mol%), THF (2 mL) and H2 (5 bar) at 150 °C during 15 h. [b] Conversion of 1 and yields of 2, 3, and 4 were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-10%) were produced following Yb(OTf)3·H2O promoted ring-opening of THF. [c] The reaction was carried out with 1 mol% of Ru catalyst (2 mol% Ru).
Table S4. Hydrogenation of benzanilide (1) with [Ru/L/Yb(OTf)3.H2O] system: screening of different phosphorus
[a] Standard reaction conditions: benzanilide 1 (100.6 mg, 0.5 mmol), Ru(acac)3 (2 mol%), ligand (4 mol%), Yb(OTf)3.H2O (4 mol%), THF (2 mL) and H2 (5 bar) at 150 °C during 15 h. [b] Conversion of 1 and yields of 2, 3, and 4 were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-10%) were produced following Yb(OTf)3·H2O promoted ring-opening of THF. [c] The main products observed were hydrogenation ring products. (Ad = adamantyl).
Table S5. Hydrogenation of benzanilide (1) with [Ru/Triphos/Yb(OTf)3.H2O] system: Influence of the solvent
[a] Standard reaction conditions: benzanilide (0.5 mmol), Ru(acac)3 (2 mol%), triphos (4 mol%), Yb(OTf)3.H2O (4 mol%), solvent (2 mL) and H2 (5 bar) at 150 °C during 15 h. [b] Conversion of 1 and yields of products 2, 3 and 4 were calculated by GC using hexadecane as internal standard. [c] Run at 45 h.
Table S6. Hydrogenation of benzanilide (1) with [Ru/Triphos/Yb(OTf)3.H2O] system: yield/time profile at 5 and 15
[a] Standard reaction conditions: benzanilide 1 (100.6 mg, 0.5 mmol), Ru catalyst (2 mol%), triphos (4 mol%), Yb(OTf)3.H2O (4 mol%), THF (2 mL) and H2 (5 or 15 bar) at 150 °C during 0.5-25 h. [b] Conversion of 1 and yields of 2, 3, and 4 were calculated by GC using hexadecane as internal standard. Variable amounts of N-phenylpyrrolidine (5-10%) were produced following Yb(OTf)3·H2O promoted ring-opening of THF.
4. ADDITIONAL SCHEMES
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3 (4 mol%)
H2 (5 bar), 150 °CTHF, 15 h
OH+
Me
Me
Ph N
OPh
H
1
NH
PhMe
Me
(70%)
NH
PhPh
2 (29%)
+
Full conversion(ref. to 1)
OHPh +
3 (69%)
Scheme S1. Reaction control experiment using 3,5-dimethylbenzyl alcohol and benzanilide 1 as starting materials. Conversion of 1 and yields of the products were calculated by GC using hexadecane as internal standard.
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3.H2O (4 mol%)
H2 (5 bar), 150 °CTHF, 15 h
OPh+ NH2Ph N
HPh
Ph
4 (1.5 eq)
H
Full conversion 2 (86%)
Scheme S2. Reaction control experiment using benzaldehyde and aniline as starting materials. Conversion of benzaldehyde and yield of product 2 were calculated by GC using hexadecane as internal standard.
205 bar of H2
conditions Conv. (%)[a]
12
(%)[a]
615 bar of N2 12
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3 (4 mol%)
150 °C, THF, 15 hOHPh +
1 eq 1.5 eq
Ph NH2 Ph NH
Ph OPh+
(%)[a]
-
45
Scheme S3. Reaction control experiments using 1-phenylethanol and aniline as starting materials. [a] Conversion of 1-phenylethanol and yield
of the products were calculated by GC using hexadecane as internal standard.
150 °C, THF, 15 h+ NH2Ph
4 (1.5 eq)
955 bar of H2
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3.H2O (4 mol%)
conditions Conv. (%)[a]
92
(%)[a]
-5 bar of H2 without Yb(OTf)3.H2O -
-5 bar of H2 without Ru(acac)3/Triphos -
OH6 NH
Ph6
5 bar of N2
5 bar of N2 without Yb(OTf)3.H2O
5 bar of N2 without Ru(acac)3/Triphos
90
--
55
6 -
Scheme S4. Reaction control experiments using octanol and aniline as starting materials. [a] Conversion of octanol and yield of the product were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-10%) were produced following Yb(OTf)3·H2O promoted ring-opening of THF.
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3 (4 mol%)
H2 (5 bar), 150 °CTHF, 15 h
O+ NH2Ph N
HPh
4 (1.5 eq) Full conversion (10%)
66
H+ N
HPh
4
6
(44%)
Scheme S5. Reaction control experiment using octanal and aniline as starting materials. Conversion of octanal and yield of the products were calculated by GC using hexadecane as internal standard.
150 °C, THF, 15 h+ NH2Ph
4 (1.5 eq)
55 bar of H2
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3.H2O (4 mol%)
conditions Conv. (%)[a]
-
(%)[a]
-5 bar of H2 without Yb(OTf)3.H2O -
-5 bar of H2 without Ru(acac)3/Triphos -
OH6 NH
Ph6
5 bar of N2
5 bar of N2 without Yb(OTf)3.H2O
5 bar of N2 without Ru(acac)3/Triphos
49
--
-
- -
O6+
(%)[a]
-
-
-
45
-
-
Scheme S6. Reaction control experiments using 2-nonanol and aniline as starting materials. [a] Conversion of 2-nonanol and yield of the products were calculated by GC using hexadecane as internal standard. In some cases, variable amounts of N-phenylpyrrolidine (5-10%) were produced following Yb(OTf)3·H2O promoted ring-opening of THF.
Ru(acac)3 (2 mol%)Triphos (4 mol%)
Yb(OTf)3 (4 mol%)
H2 (5 bar), 150 °CTHF, 15 h
OHPh + Ph N Ph
H
2 (1.5 eq)
Ph N Ph
Ph
(< 5%)Conv. = 5%3
as above+ Ph N Ph
Ph
(< 5%)
+ NH2Ph
4 (1.5 eq)
+Ph N Ph
H
2 (68%)
3 2 (1.5 eq)
Conv. = 75%
Scheme S7. Competitive experiments using N-benzylaniline 2 as starting material. Conversion of 3 and yield of the products were calculated by GC using hexadecane as internal standard.
5. CHARACTERIZATION DATA OF THE ISOLATED PRODUCTS
Ph NH
Ph
N-benzylaniline1. Isolated yield: 80%. GC-MS (m/z, M+· 183), major peaks found: 183 (75%), 106 (20%), 91
(100%), 77 (19%), 65 (16%), 51 (9%). (The NMR spectrum is consistent with the reported data). 1H NMR (300