eur. j, 2010, 16, 6509-6517 reek anti-halpern supporting

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Supporting Information

Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2010

Asymmetric Hydrogenation with Highly Active IndolPhosRh Catalysts:Kinetics and Reaction ACHTUNGTRENNUNGMechanism

Jeroen Wassenaar,[a] Mark Kuil,[b] Martin Lutz,[c] Anthony L. Spek,[c] andJoost N. H. Reek*[a]

chem_200903476_sm_miscellaneous_information.pdf


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S-1

Asymmetric hydrogenation with highly active IndolPhos-Rh

catalysts: Kinetics and reaction mechanism

Jeroen Wassenaar,[a] Mark Kuil,[b] Martin Lutz,[c] Anthony L. Spek,[c]

and Joost N. H. Reek*

,[a]

[a]Vant Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe

Achtergracht 166, 1018 WV Amsterdam, The Netherlands. [b] BASF Nederland B.V.

Catalysts, Strijkviertel 67, 3454 PK De Meern, The Netherlands. [c] Crystal and

Structural Chemistry, Bijvoet Centre for Biomolecular Research, Faculty of

Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands

E-mail: [email protected]; Fax: +31 20 5256422; Tel: +31 20 5256437

Supplementary Material

I Kinetic Experiments and Gas-uptake Profiles S-2

II Energy Diagrams for the unsaturate/dihydride and S-8

dihydride/unsaturate pathways

III NMR Spectra of IndolPhos-Rh-solvate Complexes S-9


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S-3

Determination of order in substrate for the hydrogenation of MAA. Following the

general procedure given in the experimental section, the following conditions were

used in the AMTEC experiments:


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S-4

CH2Cl2 8.00 ml

Rh(nbd)2BF4 was used as Rh-precursor (0.32 mol)

Rh/ligand 3fratio 1/ 1.1

T = 25 C

MAA (Alfa Aesar) was purified prior to use by filtration over neutral alumina eluting

with CH2Cl2.

Results:

reactor S/C conti_feed PH2 (bar) substrate (mol) conv (%) ee (%)

MK77_R4 2500 Yes 7 800 100 95.1

MK77_R6 2500 Yes 10 800 100 94.9

MK77_R7 2188 Yes 10 700 100 95.7

MK77_R8 1875 Yes 10 600 100 95.0

MK77_R9 1562 No 10 500 100 95.1

MK77_R10 1250 No 10 400 100 95.0

MK77_R12 2500 Yes 13 800 100 95.1

In all cases the (R)-enantiomer was formed as the major product

Gas-uptake profiles:


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S-5

Substrate dependency in the hydrogenation of DMI. Following the general

procedure given in the experimental section, the following conditions were used in the

AMTEC experiments:

CH2Cl2 8.00 ml

Rh(nbd)2BF4 was used as Rh-precursor (0.80 mol)Rh/ligand 3b ratio 1/ 1.1

PH2 = 10 bar

T = 25 C

Results:

reactor Substrate

(mmol)

S/ C t

(h)

conv

(%)

ee

(%)a

R1 8.0 10 000 10 100 95.9

R2 12.0 15 000 10 100 95.9

R5 16.0 20 000 10 100 96.1

R6 20.0 25 000 10 100 95.9

R13 24.0 30 000 10 100 96.2a The ee was determined by chiral GC, and in all cases the (S)-enantiomer was formed as the major

product.



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S-6

Rhodium dependency in the hydrogenation of DMI. Following the general


AMTEC experiments:

CH2Cl2 8.00 ml

Rh(nbd)2BF4 was used as Rh-precursorRh/ligand 3b ratio 1/ 1.1

DMI 8.0 mmol

PH2 = 10 bar

T = 25 C

Results:

reactor Rhodium

(mol)

mol% t

(h)

conv

(%)

ee

(%)a

R2 0.80 0.01 10 100 96.0

R4 1.60 0.02 10 100 96.1

R5 2.40 0.03 10 100 96.00

R6 3.20 0.04 10 100 95.9a

The ee was determined by chiral GC, and in all cases the (S)-enantiomer was formed as the major

product.



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S-7

Pressure dependency in the hydrogenation of DMI. Following the general


AMTEC experiments:

CH2Cl2 8.00 ml

Rh(nbd)2BF4 was used as Rh-precursor (0.80 mol)Rh/ligand 3b ratio 1/ 1.1

DMI 16.0 mmol

T = 25 C

Results:

reactor Pressure H2

(bar)

mol% t

(h)

conv

(%)

ee

(%)a

R4 10 0.005 10 100 96.2

R8 20 0.005 10 100 96.1

R16 30 0.005 10 100 95.8a

The ee was determined by chiral GC, and in all cases the (S)-enantiomer was formed as the major

product.



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S-8

II Energy Diagrams for the unsaturate/dihydride and

dihydride/unsaturate pathways

[(P-P)Rh(s)2]+

A

COOR1

NH

O

R2

(P-P)Rh

+

1B

COOR1

NH

O

R2

(P-P)(H)2Rh

+

1C

NH

O

R2

(P-P)(H)(s)Rh

+

1D COOR1

H

[(P-P)Rh(s)2]+

A

R1OOC NHCOR2(S)

+NHCOR2R1O2C

H2

+

+

+ H2

E

Figure S-1. Schematic energy diagram for the unsaturate/dihydride pathway.

Depending on the relative barrier heights, oxidative addition of H2 or migratory

insertion is rate-determining.

[(P-P)Rh(s)2]+

A

[(P-P)Rh(s)2]+

A

R1OOC NHCOR2

(S)+

NHCOR2R1O2C

H2

+

+

E

[(P-P)Rh(H)2(s)2]+

2B

NHCOR2R1O2C+

COOR1

NH

O

R2

(P-P)(H)2Rh

+

2C

NH

O

R2

(P-P)(H)(s)Rh

+

2D COOR1

H

Figure S-2. Schematic energy diagram for the dihydride/unsaturate pathway.

Depending on the relative barrier heights, alkene coordination or migratory insertion

is rate-determining.


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S-9

II NMR Spectra of IndolPhos-Rh-solvate Complexes

31P{

1H} NMR spectrum (202 MHz; CDCl3; 298 K) of [Rh(3f)(nbd)]BF4 (5).

31P{

1H} NMR spectrum (202 MHz; CD2Cl2; 298 K) of [Rh(3f)(nbd)]BF4 under 10

bar H2, after vigorous manual shaking. The broad signals are proposed to stem from

the CD2Cl2 solvate complex, [Rh(3f)(CD2Cl2)2]BF4.


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S-10

1H NMR spectrum (500 MHz; CDCl3; 298 K) of [Rh(3b)(MeCN)2]BF4.

13C NMR spectrum (126 MHz; CDCl3; 298 K) of [Rh(3b)(MeCN)2]BF4.


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S-11

31P

{

1H} NMR spectrum (500 MHz; CDCl3; 298 K) of [Rh(3b)(MeCN)2]BF4.

1H NMR spectrum (500 MHz; CD3OD; 253 K) of [Rh(3f)(nbd)]BF4 under 5 bar H2,

after vigorous manual shaking. The signals of the CD3OD solvate complex,

[Rh(3f)(CD3OD)2]BF4, can be clearly distinguished. Some signals are obscured by

norbornane. Dissolved molecular hydrogen shows up as a singlet at 5.4 ppm.


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S-12

31P

{

1H} NMR spectrum (202 MHz; CD3OD; 253 K) of [Rh(3f)(nbd)]BF4 under 5

bar H2, after vigorous manual shaking. The CD3OD solvate complex,

[Rh(3f)(CD3OD)2]BF4, shows up as two doublets-of-doublets.

eur. j, 2010, 16, 6509-6517 reek anti-halpern supporting

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