Cooperative effect of two metals: CoPd(OAc)4-catalyzed C-H amination and aziridination

Article abstract of DOI:10.1002/chem.201304633

The first Co/Pd-cocatalyzed intramolecular C-H amination and aziridination reactions were developed. Sulfamate esters were converted to oxathiazinanes by using CoPd(OAc)₄ as catalyst and PhI(OAc)₂ as oxidant. The mutual presence of b

Full text of DOI:10.1002/chem.201304633

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
Cooperative Effect of Two Metals: CoPd(OAc) -Catalyzed CÀH
4
Amination and Aziridination
[
a]
Guan-Hao Huang, Jian-Min Li, Jing-Jyun Huang, Jyun-Dai Lin, and Gary Jing Chuang*
chem_201304633_sm_miscellaneous_information.pdf

Supporting Information
S1
Table of Contents
Materials and Methods .................................................................................................................... 3
Experimental Data:.......................................................................................................................... 3
4
Synthesis of CoPd(OAc) ............................................................................................................ 3
Optimization of the Reaction Condition...................................................................................... 4
Effect of oxidant loading:........................................................................................................ 4
Effect of concentration: ........................................................................................................... 4
Solvent effect:.......................................................................................................................... 5
Source of Palladium: ............................................................................................................... 6
Effect of base:.......................................................................................................................... 6
X-ray Crystallographic Analysis ................................................................................................. 7
4
ORTEP of CoPd(OAc) ........................................................................................................... 7
ORTEP of 12 ......................................................................................................................... 21
ORTEP of 31 ......................................................................................................................... 27
Spectroscopic Data.................................................................................................................... 34
1
H NMR of 2 ......................................................................................................................... 34
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3
C and DEPT NMR of 2....................................................................................................... 35
H NMR of 4 ......................................................................................................................... 36
H NMR of 6 ......................................................................................................................... 37
3
C and DEPT NMR of 6....................................................................................................... 38
H NMR of 8 ......................................................................................................................... 39
H NMR of 1 (H/D) in KIE study.......................................................................................... 40
3
C NMR of 1(H/D) in KIE study ......................................................................................... 41
H NMR of 2(H/D) in KIE study........................................................................................... 42
3
C NMR of 2(H/D) in KIE study ......................................................................................... 43
H NMR of 10 ....................................................................................................................... 44
3
C and DEPT NMR of 10..................................................................................................... 45
H NMR of 12 ....................................................................................................................... 46
3
C NMR of 12 ...................................................................................................................... 47
H NMR of 13 ....................................................................................................................... 48
3
C NMR of 13 ...................................................................................................................... 49
H NMR of 15 ....................................................................................................................... 50

Supporting Information
S2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3
C NMR of 15 ...................................................................................................................... 51
H NMR of 17 ....................................................................................................................... 52
3
C and DEPT NMR of 17..................................................................................................... 53
H NMR of 26 ....................................................................................................................... 54
3
C and DEPT NMR of 26..................................................................................................... 55
H NMR of 27 ....................................................................................................................... 56
H NMR of 28 ....................................................................................................................... 57
3
C and DEPT NMR of 28..................................................................................................... 58
H NMR of 29 ....................................................................................................................... 59
H NMR of 30 ....................................................................................................................... 60
3
C and DEPT NMR of 30..................................................................................................... 61
H NMR of 31 ....................................................................................................................... 62
3
C and DEPT NMR of 31..................................................................................................... 63
H NMR of 32 ....................................................................................................................... 64
H NMR of 33 ....................................................................................................................... 65
3
C and DEPT NMR of 33..................................................................................................... 66
H NMR of 34 ....................................................................................................................... 67

Supporting Information
S3
Materials and Methods
All reactions were carried out under an inert nitrogen atmosphere unless otherwise indicated.
Solvents other than methanol were dried by passage through alumina. Except as indicated
otherwise, reactions were magnetically stirred and monitored by thin layer chromatography
(TLC) with Merck 5735 DC-plaskfolien Kieselgel 60 F254 plates and visualized by fluorescence
quenching under UV light. In addition, TLC plates were stained using ceric ammonium
molybdate or potassium permanganate stain. Flash chromatography was performed on Merck Art.
7
734 Kieselgel 60 (70~230 mesh) using a forced flow of eluent at 0.3–0.5 bar pressure.
Concentration under reduced pressure was performed by rotary evaporation at 25–30 ºC at
appropriate pressure. Purified compounds were further dried under high vacuum (0.01–0.05 Torr).
1
13
NMR spectra were recorded on a Bruker ACE-300( H, 300 MHz; C, 75 MHz) or Bruker ACE
1
13
13
II-400MHz FT-NMR( H, 400 MHz; C, 100MHz) spectrometer. C NMR spectra were recorded
1
H decoupled. Chemical shifts are reported in ppm with the solvent resonance as the internal
standard. Data are reported as follows: s = singlet, d = doublet, t = triplet, q = quartet, h = heptet,
m = multiplet, br = broad; coupling constants in Hz; integration. High-resolution mass spectra
were obtained on Waters Micromass Q-TOF Premier Mass spectrometers. Chemicals were
purchased from Aldrich, Alfa Aesar, Frontier Scientific, Matrix Scientific, or Boron Molecular
and used as received. NMR spectroscopic data of known compounds correspond to the data given
in the appropriate references.
Experimental Data:
1
All of the sulfamate esters were synthesized according to the reported method .
Synthesis of CoPd(OAc)4
Co(OAc) + Pd(OAc)
CoPd(OAc)4
2
2
AcOH, reflux
To Co(OAc)
2
(tetrahydrate) (498 mg, 2.00 mmol, 1.00 equiv) in glacial acetic acid (2 mL) at rt
was added Pd(OAc)
2
(450 mg, 2.00 mmol, 1.00 equiv). The reaction mixture was heated to
reflux and stirred for 1.5 hr. The solution was then filtered while hot through filter paper. The
filtrate was concentrated in vacuo and the residue was washed with ether to afford 523 mg of the
4
title compound as brown powder (55% yield). The structure of CoPd(OAc) was assigned by X-
ray diffraction analysis of the crystal obtained from recrystallation in THF/n-Hexane and was
found to be identical to the reported paddlewheel structure. (ORTEP and X-ray data are shown in
X-ray Crystallographic Analysis section)
1
K. W. Fiori, C. G. Espino, H. B. Brodsky, J. Du Bois, Tetrahedron, 2009, 65, 3042－3051.

Supporting Information
S4
Optimization of the Reaction Condition
Effect of oxidant loading:
5
mol % PdCo(OAc)4
O
O
O
O
PhI(OAc)2
S
S
H N
O
HN
O
2
MgO
o
CH Cl , 40 C, 4h
2
2
1
2
P/SM(a)(%)
54 : 46
Entry
1
PhI(OAc)
(eq)
2
MgO(eq)
3.0
1.5
2
3
2.0
2.5
4.2
5.3
55 : 45
75 : 25
4
5
3.0
3.5
6.3
7.3
82 : 18
78 : 22
1
(
a)Ratio determined by H NMR of the crude mixture
Effect of concentration:
5
mol % PdCo(OAc)4
PhI(OAc)2
O
O
O
O
S
S
H N
O
HN
O
2
MgO
o
CH Cl , 40 C, 4h
2
2
1
2
Entry
concentration of 1(M)
P/SM(%)
1
2
0.04
0.05
54 : 46
52 : 48
3
4
5
6
7
0.06
0.08
0.1
60 : 40
61 : 39
80 : 20
76 : 24
63 : 37
0.125
0.16

Supporting Information
S5
Solvent effect:
5
mol % PdCo(OAc)4
PhI(OAc)2
O
O
O
O
S
S
H N
O
HN
O
2
MgO
o
solvent, 40 C, 4h
1
2
Entry
1
solvent
P/SM(%)
16 : 84
Ethyl acetate
2
3
Hexanes
Ether
37 : 63
0 : 100
4
5
6
Toluene
0 : 100
0 : 100
9 : 91
Triethyl amine
Acetonitrile
7
8
9
1,2-Dichloroethane
Chloroform
1,4-Dioxane
THF
57 : 43
0 : 57
0 : 100
0 : 100
0 : 100
25 : 75
82 : 18
10
11
12
13
Benzene
1-Ethyl-3-methylimi
-
dazolium acetate(ionic liquid)
Dichloromethane

Supporting Information
S6
Source of Palladium:
5
mol % PdCo(OAc)4
PhI(OAc)2
O
O
O
O
S
S
H N
O
HN
O
2
MgO
o
solvent, 40 C, 4h
1
2
P/SM(a)(%)
Entry
1
brands
UR
58 : 42
2
3
4
Seedchem
Alfa
65 : 35
80 : 20
100 : 0
Strem
Effect of base:
5
mol % PdCo(OAc)4
O
O
O
O
3
eq PhI(OAc)2
S
S
H N
O
HN
O
2
Base
o
CH Cl , 40 C
2
2
1
2
Entry
1
Base
Reaction time (hr)
4
P/M (%)
K2CO3
Na2CO3
MgO
0 : 100
39 : 61
82 : 18
67 : 33
73 :27
99 : 1
2
3
4
5
6
7
4
4
no base
no base
no base
MgO
4
10
12
12
82 : 18
*
Pd from Alfa

Supporting Information
S7
X-ray Crystallographic Analysis
ORTEP of CoPd(OAc)
4

Supporting Information
S8
Table 1. Crystal data and structure refinement for CoPd(OAc)4.
Identification code
Empirical formula
Formula weight
Temperature
a15626
C8 H14 Co O9 Pd
419.52
200(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Triclinic
P -1
Unit cell dimensions
a = 8.5670(7) Å
b = 11.1201(10) Å
c = 14.5790(14) Å
ꢀ= 86.717(4)°.
ꢀ= 88.185(4)°.
ꢀ = 78.878(3)°.
Volume
1360.3(2) Å3
4
Z
Density (calculated)
Absorption coefficient
F(000)
2.049 Mg/m3
2.577 mm-1
828
Crystal size
0.48 x 0.27 x 0.02 mm3
1.87 to 25.14°.
Theta range for data collection
Index ranges
-10<=h<=9, -13<=k<=13, -16<=l<=17
11977
Reflections collected
Independent reflections
Completeness to theta = 25.14°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
4750 [R(int) = 0.0412]
97.4 %
multi-scan
0.9503 and 0.3710
Full-matrix least-squares on F2
4750 / 0 / 343
1.030
R1 = 0.0403, wR2 = 0.0785
R1 = 0.0564, wR2 = 0.0850
0.773 and -0.672 e.Å-3

Supporting Information
S9
4
2
3
Table 2. Atomic coordinates ( x 10 ) and equivalent isotropic displacement parameters (Å x 10 )
ij
for CoPd(OAc)4. U(eq) is defined as one third of the trace of the orthogonalized U tensor.
_
_______________________________________________________________________________
U(eq)
_______________________________________________________________________________
x
y
z
_
C(1)
2102(7)
2477(7)
-1166(7)
-2837(6)
1523(6)
1517(7)
4657(7)
6331(7)
2831(7)
2975(8)
498(7)
7409(5)
7355(5)
8687(5)
9419(5)
7555(5)
7643(5)
6316(5)
5658(5)
2493(5)
2550(6)
1111(5)
393(5)
6926(3)
5920(3)
8618(3)
8596(4)
10519(3)
11539(3)
8856(3)
8972(4)
4340(3)
3310(3)
6158(3)
6195(4)
7959(4)
8986(4)
6184(4)
6250(4)
7327(2)
7314(2)
8723(2)
8522(2)
10052(2)
10182(2)
8781(2)
8852(2)
8728(2)
4743(2)
4733(2)
6273(2)
6017(2)
7482(2)
22(1)
33(2)
20(1)
26(1)
20(1)
27(1)
24(1)
32(2)
23(1)
37(2)
22(1)
33(2)
28(1)
52(2)
28(1)
41(2)
24(1)
22(1)
24(1)
23(1)
26(1)
20(1)
26(1)
27(1)
29(1)
27(1)
26(1)
28(1)
27(1)
30(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(12)
O(13)
O(14)
-829(7)
2937(7)
3072(8)
5126(8)
6470(7)
2557(4)
1389(4)
-966(4)
-43(4)
2000(5)
1784(6)
3470(6)
4140(6)
8265(3)
6624(3)
7548(3)
9306(3)
8448(3)
6648(3)
5713(3)
7489(3)
4739(3)
1612(3)
3285(3)
2246(3)
506(3)
1954(4)
1137(4)
3583(4)
4430(4)
568(4)
3792(5)
1835(4)
150(4)
1893(5)
3645(5)
1135(3)

Supporting Information
S10
O(15)
O(16)
O(17)
O(18)
Co(1)
Co(2)
Pd(1)
Pd(2)
2161(4)
5483(4)
3758(5)
250(4)
3010(3)
2295(4)
4083(3)
5026(3)
6385(1)
3395(1)
8397(1)
1372(1)
7629(2)
6216(3)
6090(3)
6337(2)
8753(1)
6189(1)
8682(1)
6113(1)
25(1)
30(1)
29(1)
26(1)
17(1)
20(1)
18(1)
22(1)
1182(1)
1719(1)
2201(1)
3712(1)
________________________________________________________________________________

Supporting Information
S11
Table 3. Bond lengths [Å] and angles [°] for CoPd(OAc)4.
_____________________________________________________
C(1)-O(2)
1.259(6)
1.273(6)
1.492(6)
0.9800
C(1)-O(1)
C(1)-C(2)
C(2)-H(2A)
C(2)-H(2B)
C(2)-H(2C)
C(3)-O(3)
0.9800
0.9800
1.246(6)
1.287(6)
1.505(7)
0.9800
C(3)-O(4)
C(3)-C(4)
C(4)-H(4A)
C(4)-H(4B)
C(4)-H(4C)
C(5)-O(6)
0.9800
0.9800
1.251(6)
1.278(6)
1.496(6)
0.9800
C(5)-O(5)
C(5)-C(6)
C(6)-H(6A)
C(6)-H(6B)
C(6)-H(6C)
C(7)-O(7)
0.9800
0.9800
1.249(6)
1.281(6)
1.489(8)
0.9800
C(7)-O(8)
C(7)-C(8)
C(8)-H(8A)
C(8)-H(8B)
C(8)-H(8C)
C(9)-O(11)
C(9)-O(10)
C(9)-C(10)
C(10)-H(10A)
C(10)-H(10B)
C(10)-H(10C)
C(11)-O(12)
C(11)-O(13)
C(11)-C(12)
0.9800
0.9800
1.252(6)
1.279(6)
1.501(7)
0.9800
0.9800
0.9800
1.259(6)
1.270(6)
1.508(7)

Supporting Information
S12
C(12)-H(12A)
C(12)-H(12B)
C(12)-H(12C)
C(13)-O(14)
C(13)-O(15)
C(13)-C(14)
C(14)-H(14A)
C(14)-H(14B)
C(14)-H(14C)
C(15)-O(17)
C(15)-O(16)
C(15)-C(16)
C(16)-H(16A)
C(16)-H(16B)
C(16)-H(16C)
O(1)-Pd(1)
0.9800
0.9800
0.9800
1.267(6)
1.267(6)
1.506(7)
0.9800
0.9800
0.9800
1.245(7)
1.281(7)
1.495(8)
0.9800
0.9800
0.9800
1.998(3)
2.106(3)
2.035(4)
2.006(4)
2.004(3)
2.118(3)
2.050(4)
1.996(4)
2.002(3)
0.9169
O(2)-Co(1)
O(3)-Co(1)
O(4)-Pd(1)
O(5)-Pd(1)
O(6)-Co(1)
O(7)-Co(1)
O(8)-Pd(1)
O(9)-Co(1)
O(9)-H(9A)
O(9)-H(9B)
O(10)-Pd(2)
O(11)-Co(2)
O(12)-Co(2)
O(13)-Pd(2)
O(14)-Pd(2)
O(15)-Co(2)
O(16)-Pd(2)
O(17)-Co(2)
O(18)-Co(2)
0.8957
2.000(3)
2.131(3)
2.023(4)
1.997(4)
1.999(3)
2.149(4)
2.003(4)
2.036(4)
2.017(4)

Supporting Information
S13
O(18)-H(18A)
O(18)-H(18B)
Co(1)-Pd(1)
Co(2)-Pd(2)
0.8806
0.8837
2.5501(8)
2.5539(8)
O(2)-C(1)-O(1)
O(2)-C(1)-C(2)
125.0(5)
119.1(5)
115.9(5)
109.5
O(1)-C(1)-C(2)
C(1)-C(2)-H(2A)
C(1)-C(2)-H(2B)
H(2A)-C(2)-H(2B)
C(1)-C(2)-H(2C)
H(2A)-C(2)-H(2C)
H(2B)-C(2)-H(2C)
O(3)-C(3)-O(4)
O(3)-C(3)-C(4)
109.5
109.5
109.5
109.5
109.5
125.1(5)
118.8(5)
116.2(5)
109.5
O(4)-C(3)-C(4)
C(3)-C(4)-H(4A)
C(3)-C(4)-H(4B)
H(4A)-C(4)-H(4B)
C(3)-C(4)-H(4C)
H(4A)-C(4)-H(4C)
H(4B)-C(4)-H(4C)
O(6)-C(5)-O(5)
O(6)-C(5)-C(6)
109.5
109.5
109.5
109.5
109.5
124.8(5)
120.0(5)
115.2(4)
109.5
O(5)-C(5)-C(6)
C(5)-C(6)-H(6A)
C(5)-C(6)-H(6B)
H(6A)-C(6)-H(6B)
C(5)-C(6)-H(6C)
H(6A)-C(6)-H(6C)
H(6B)-C(6)-H(6C)
O(7)-C(7)-O(8)
O(7)-C(7)-C(8)
109.5
109.5
109.5
109.5
109.5
124.6(5)
119.4(5)
115.9(5)
O(8)-C(7)-C(8)

Supporting Information
S14
C(7)-C(8)-H(8A)
109.5
C(7)-C(8)-H(8B)
109.5
H(8A)-C(8)-H(8B)
C(7)-C(8)-H(8C)
109.5
109.5
H(8A)-C(8)-H(8C)
H(8B)-C(8)-H(8C)
O(11)-C(9)-O(10)
109.5
109.5
125.5(5)
119.7(5)
114.8(5)
109.5
O(11)-C(9)-C(10)
O(10)-C(9)-C(10)
C(9)-C(10)-H(10A)
C(9)-C(10)-H(10B)
H(10A)-C(10)-H(10B)
C(9)-C(10)-H(10C)
H(10A)-C(10)-H(10C)
H(10B)-C(10)-H(10C)
O(12)-C(11)-O(13)
O(12)-C(11)-C(12)
O(13)-C(11)-C(12)
C(11)-C(12)-H(12A)
C(11)-C(12)-H(12B)
H(12A)-C(12)-H(12B)
C(11)-C(12)-H(12C)
H(12A)-C(12)-H(12C)
H(12B)-C(12)-H(12C)
O(14)-C(13)-O(15)
O(14)-C(13)-C(14)
O(15)-C(13)-C(14)
C(13)-C(14)-H(14A)
C(13)-C(14)-H(14B)
H(14A)-C(14)-H(14B)
C(13)-C(14)-H(14C)
H(14A)-C(14)-H(14C)
H(14B)-C(14)-H(14C)
O(17)-C(15)-O(16)
O(17)-C(15)-C(16)
109.5
109.5
109.5
109.5
109.5
125.3(5)
118.3(5)
116.4(5)
109.5
109.5
109.5
109.5
109.5
109.5
124.4(5)
116.0(5)
119.6(5)
109.5
109.5
109.5
109.5
109.5
109.5
124.8(6)
118.3(6)

Supporting Information
S15
O(16)-C(15)-C(16)
C(15)-C(16)-H(16A)
C(15)-C(16)-H(16B)
H(16A)-C(16)-H(16B)
C(15)-C(16)-H(16C)
H(16A)-C(16)-H(16C)
H(16B)-C(16)-H(16C)
C(1)-O(1)-Pd(1)
116.9(6)
109.5
109.5
109.5
109.5
109.5
109.5
119.8(3)
122.7(3)
125.2(3)
117.8(3)
119.9(3)
123.6(3)
126.8(4)
116.9(3)
128.0
C(1)-O(2)-Co(1)
C(3)-O(3)-Co(1)
C(3)-O(4)-Pd(1)
C(5)-O(5)-Pd(1)
C(5)-O(6)-Co(1)
C(7)-O(7)-Co(1)
C(7)-O(8)-Pd(1)
Co(1)-O(9)-H(9A)
Co(1)-O(9)-H(9B)
H(9A)-O(9)-H(9B)
C(9)-O(10)-Pd(2)
C(9)-O(11)-Co(2)
C(11)-O(12)-Co(2)
C(11)-O(13)-Pd(2)
C(13)-O(14)-Pd(2)
C(13)-O(15)-Co(2)
C(15)-O(16)-Pd(2)
C(15)-O(17)-Co(2)
Co(2)-O(18)-H(18A)
Co(2)-O(18)-H(18B)
H(18A)-O(18)-H(18B)
O(9)-Co(1)-O(3)
119.5
108.3
120.0(3)
122.3(4)
124.9(4)
117.8(3)
119.6(4)
123.7(3)
117.8(4)
125.3(4)
121.8
115.0
109.4
102.41(15)
95.20(15)
162.39(15)
94.61(14)
89.66(14)
88.50(14)
O(9)-Co(1)-O(7)
O(3)-Co(1)-O(7)
O(9)-Co(1)-O(2)
O(3)-Co(1)-O(2)
O(7)-Co(1)-O(2)

Supporting Information
S16
O(9)-Co(1)-O(6)
O(3)-Co(1)-O(6)
O(7)-Co(1)-O(6)
O(2)-Co(1)-O(6)
O(9)-Co(1)-Pd(1)
O(3)-Co(1)-Pd(1)
O(7)-Co(1)-Pd(1)
O(2)-Co(1)-Pd(1)
O(6)-Co(1)-Pd(1)
O(18)-Co(2)-O(12)
O(18)-Co(2)-O(17)
O(12)-Co(2)-O(17)
O(18)-Co(2)-O(11)
O(12)-Co(2)-O(11)
O(17)-Co(2)-O(11)
O(18)-Co(2)-O(15)
O(12)-Co(2)-O(15)
O(17)-Co(2)-O(15)
O(11)-Co(2)-O(15)
O(18)-Co(2)-Pd(2)
O(12)-Co(2)-Pd(2)
O(17)-Co(2)-Pd(2)
O(11)-Co(2)-Pd(2)
O(15)-Co(2)-Pd(2)
O(8)-Pd(1)-O(1)
O(8)-Pd(1)-O(5)
O(1)-Pd(1)-O(5)
O(8)-Pd(1)-O(4)
O(1)-Pd(1)-O(4)
O(5)-Pd(1)-O(4)
O(8)-Pd(1)-Co(1)
O(1)-Pd(1)-Co(1)
O(5)-Pd(1)-Co(1)
O(4)-Pd(1)-Co(1)
O(13)-Pd(2)-O(14)
101.69(13)
86.34(14)
90.55(14)
163.69(13)
174.27(10)
82.17(10)
80.23(10)
81.89(10)
81.91(9)
100.98(15)
95.65(15)
163.32(15)
101.80(14)
89.78(14)
88.03(15)
95.73(14)
89.09(14)
88.01(15)
162.33(14)
175.21(11)
81.84(11)
81.48(11)
81.98(10)
80.40(10)
88.23(15)
88.58(15)
176.61(15)
179.53(14)
92.20(14)
90.99(15)
90.82(11)
89.32(10)
89.60(10)
88.99(10)
90.76(15)

Supporting Information
S17
O(13)-Pd(2)-O(10)
O(14)-Pd(2)-O(10)
O(13)-Pd(2)-O(16)
O(14)-Pd(2)-O(16)
O(10)-Pd(2)-O(16)
O(13)-Pd(2)-Co(2)
O(14)-Pd(2)-Co(2)
O(10)-Pd(2)-Co(2)
O(16)-Pd(2)-Co(2)
89.60(15)
179.63(16)
178.04(15)
89.06(16)
90.59(15)
88.93(11)
90.73(10)
89.39(11)
89.12(11)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Supporting Information
S18
2
3
Table 4. Anisotropic displacement parameters (Å x 10 )for CoPd(OAc)4. The anisotropic
displacement factor exponent takes the form: -2ꢀ [ h a* U + ... + 2 h k a* b* U12
2
2
2
11
]
_
_____________________________________________________________________________
U11 U22 U33 U23 U13 U12
_____________________________________________________________________________
_
C(1)
26(3)
45(4)
22(3)
24(3)
16(3)
42(4)
23(4)
18(3)
22(3)
53(5)
29(4)
36(4)
28(4)
57(5)
34(4)
32(4)
33(2)
30(2)
19(2)
19(2)
37(3)
28(2)
20(2)
17(2)
38(3)
28(2)
32(2)
27(2)
28(2)
36(3)
21(3)
30(4)
26(4)
23(3)
22(3)
24(3)
33(4)
35(4)
33(4)
46(4)
21(3)
24(4)
29(4)
60(5)
33(4)
49(4)
21(2)
22(2)
15(2)
16(2)
21(2)
17(2)
21(2)
24(2)
20(2)
30(2)
27(2)
22(2)
21(2)
27(2)
19(3)
24(3)
13(3)
32(3)
21(3)
18(3)
17(3)
42(4)
16(3)
15(3)
17(3)
38(3)
26(3)
26(3)
19(3)
48(4)
19(2)
15(2)
37(2)
33(2)
22(2)
17(2)
36(2)
42(2)
31(2)
24(2)
18(2)
35(2)
31(2)
22(2)
1(2)
-3(3)
-3(2)
-6(3)
-4(2)
-2(2)
4(2)
-3(2)
1(3)
-2(3)
-10(3)
-5(3)
-6(3)
-3(3)
-14(3)
-8(3)
-3(3)
-11(3)
-13(3)
-8(3)
-10(3)
-1(3)
21(4)
-8(3)
-17(3)
-11(2)
-7(2)
-4(2)
-2(2)
-13(2)
-9(2)
-5(2)
-9(2)
-13(2)
-5(2)
-1(2)
-5(2)
-5(2)
7(2)
C(2)
C(3)
-3(2)
-2(3)
0(2)
C(4)
C(5)
C(6)
2(3)
C(7)
4(2)
C(8)
4(3)
1(3)
C(9)
0(3)
-4(2)
1(3)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
O(10)
O(11)
O(12)
O(13)
O(14)
-4(3)
3(2)
-5(2)
1(3)
3(3)
0(3)
-5(3)
-2(3)
0(3)
4(3)
-4(3)
-11(3)
0(2)
0(3)
2(2)
2(2)
-2(2)
-2(2)
-2(2)
4(2)
-1(2)
-1(2)
-3(2)
-2(2)
-1(2)
2(2)
3(2)
0(2)
-5(2)
16(2)
1(2)
-6(2)
-2(2)
-1(2)
-2(2)
-1(2)
0(2)
-5(2)
2(2)
-1(2)
-2(2)

Supporting Information
S19
O(15)
O(16)
O(17)
O(18)
Co(1)
Co(2)
Pd(1)
Pd(2)
31(2)
21(2)
23(2)
30(2)
20(1)
20(1)
20(1)
23(1)
24(2)
29(3)
26(2)
20(2)
14(1)
19(1)
15(1)
20(1)
19(2)
39(2)
37(2)
27(2)
19(1)
21(1)
19(1)
21(1)
-5(2)
-7(2)
0(2)
-1(2)
-2(2)
-5(2)
-9(2)
1(1)
-4(2)
-2(2)
-5(2)
-3(2)
-6(1)
-2(1)
-7(1)
0(1)
-8(2)
-2(1)
-2(1)
-1(1)
-2(1)
-2(1)
0(1)
-1(1)
______________________________________________________________________________

Supporting Information
S20
4
2
3
Table 5. Hydrogen coordinates ( x 10 ) and isotropic displacement parameters (Å x 10 )
for CoPd(OAc)4.
_
_______________________________________________________________________________
U(eq)
_______________________________________________________________________________
x
y
z
_
H(2A)
H(2B)
3045
1486
3146
-2806
-3397
-3398
1860
2248
439
8014
7457
6560
10295
9262
9177
8400
6935
7652
6256
5172
5112
1877
3336
2475
-472
722
5723
5582
5796
8517
9174
8082
11685
11812
11789
9029
8436
9528
3114
3095
3050
6097
5715
6798
9288
9150
9186
6327
6779
5687
9177
8370
5878
6644
49
49
49
39
39
39
41
41
41
49
49
49
56
56
56
49
49
49
78
78
78
62
62
62
26
26
26
26
H(2C)
H(4A)
H(4B)
H(4C)
H(6A)
H(6B)
H(6C)
H(8A)
H(8B)
7022
6673
6400
3811
3248
1959
-388
-1593
-1368
2503
4196
2604
7469
6283
6538
47
H(8C)
H(10A)
H(10B)
H(10C)
H(12A)
H(12B)
H(12C)
H(14A)
H(14B)
H(14C)
H(16A)
H(16B)
H(16C)
H(9A)
H(9B)
463
2511
1628
1073
3547
4659
4655
4348
4172
5417
5557
1122
-313
647
H(18A)
H(18B)
________________________________________________________________________________

Supporting Information
S21
ORTEP of 12
O
O
S
H
HN
Ph
O
Me
H
Me
12
Table 1. Crystal data and structure refinement for 12.
Identification code
Empirical formula
Formula weight
Temperature
2
C13 H19 N O3 S
269.35
296(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Orthorhombic
P b c a
Unit cell dimensions
a = 16.9766(5) Å
b = 6.8519(2) Å
c = 25.7008(9) Å
2989.57(16) Å3
α= 90°.
β= 90°.
γ = 90°.
Volume

Supporting Information
S22
Z
8
Density (calculated)
Absorption coefficient
F(000)
1.197 Mg/m3
0.217 mm-1
1152
Crystal size
0.20 x 0.20 x 0.20 mm3
1.58 to 28.46°.
Theta range for data collection
Index ranges
-22<=h<=22, -9<=k<=9, -34<=l<=20
26646
Reflections collected
Independent reflections
Completeness to theta = 28.46°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
3748 [R(int) = 0.0853]
99.2 %
Semi-empirical from equivalents
0.9579 and 0.9579
Full-matrix least-squares on F2
3748 / 0 / 163
0.977
R1 = 0.0589, wR2 = 0.1305
R1 = 0.1621, wR2 = 0.1698
0.316 and -0.301 e.Å-3
Largest diff. peak and hole

Supporting Information
S23
4
2
3
Table 2. Atomic coordinates ( x 10 ) and equivalent isotropic displacement parameters (Å x 10 )
ij
for 12. U(eq) is defined as one third of the trace of the orthogonalized U tensor.
_
_______________________________________________________________________________
U(eq)
_______________________________________________________________________________
x
y
z
_
S(1)
3943(1)
3896(1)
4207(1)
3176(1)
4570(1)
3832(2)
3555(3)
3243(3)
3215(2)
3494(2)
3798(2)
3445(2)
3723(2)
3695(2)
4004(2)
3983(3)
4337(4)
3186(4)
350(1)
1445(3)
1955(3)
-295(3)
-1028(3)
6644(7)
5547(9)
3759(9)
3049(6)
4134(5)
5956(6)
3307(4)
4652(4)
3724(4)
5021(5)
4165(8)
5642(9)
3579(17)
4450(1)
5001(1)
4055(1)
4310(1)
4467(1)
6161(2)
6563(2)
6462(2)
5961(2)
5550(1)
5655(2)
5008(1)
4582(1)
4050(1)
3626(1)
3081(2)
2699(2)
2921(2)
57(1)
54(1)
58(1)
70(1)
73(1)
104(1)
114(2)
117(2)
90(1)
59(1)
78(1)
52(1)
56(1)
57(1)
80(1)
132(2)
197(3)
290(6)
N(1)
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(13)
C(14)
________________________________________________________________________________

Supporting Information
S24
Table 3. Bond lengths [Å] and angles [°] for 12.
_____________________________________________________
S(1)-O(2)
S(1)-O(3)
S(1)-O(1)
S(1)-N(1)
N(1)-C(7)
O(1)-C(9)
C(1)-C(2)
C(1)-C(6)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(5)-C(7)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
C(10)-C(11)
C(11)-C(14)
C(11)-C(13)
1.4211(19)
1.4232(19)
1.563(2)
1.604(3)
1.487(3)
1.491(3)
1.361(6)
1.384(5)
1.360(6)
1.376(5)
1.376(4)
1.379(5)
1.506(4)
1.507(4)
1.506(4)
1.502(4)
1.518(6)
1.469(7)
1.533(7)
O(2)-S(1)-O(3)
O(2)-S(1)-O(1)
O(3)-S(1)-O(1)
O(2)-S(1)-N(1)
O(3)-S(1)-N(1)
O(1)-S(1)-N(1)
C(7)-N(1)-S(1)
C(9)-O(1)-S(1)
119.08(13)
108.45(12)
105.79(12)
108.85(13)
108.77(13)
104.99(12)
115.91(19)
114.21(17)

Supporting Information
S25
C(2)-C(1)-C(6)
C(3)-C(2)-C(1)
C(2)-C(3)-C(4)
C(5)-C(4)-C(3)
C(4)-C(5)-C(6)
C(4)-C(5)-C(7)
C(6)-C(5)-C(7)
C(5)-C(6)-C(1)
N(1)-C(7)-C(5)
N(1)-C(7)-C(8)
C(5)-C(7)-C(8)
C(9)-C(8)-C(7)
O(1)-C(9)-C(10)
O(1)-C(9)-C(8)
C(10)-C(9)-C(8)
C(9)-C(10)-C(11)
C(14)-C(11)-C(10)
C(14)-C(11)-C(13)
C(10)-C(11)-C(13)
120.7(4)
119.1(4)
120.7(5)
121.1(4)
117.9(3)
119.3(3)
122.9(3)
120.5(4)
107.8(2)
110.8(2)
115.1(3)
113.0(2)
106.4(2)
108.5(2)
113.4(3)
115.7(3)
112.7(5)
111.3(5)
109.0(4)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Supporting Information
S26
4
2
3
Table 4. Hydrogen coordinates ( x 10 ) and isotropic displacement parameters (Å x 10 )
for 12.
_
_______________________________________________________________________________
U(eq)
_______________________________________________________________________________
x
y
z
_
H(1B)
4118
4046
3580
3046
3005
3983
2892
3397
4260
3152
4544
3700
4316
4337
4868
4029
3207
2850
2981
985
7869
6014
3008
1817
6730
2992
5814
5052
3343
5360
6220
2998
5098
5937
6816
3004
4705
2645
5276
6227
6902
6733
5900
5384
4938
4580
4655
3970
3707
3626
3079
2355
2801
2703
2581
2914
3164
65
125
137
140
108
94
H(1A)
H(2A)
H(3A)
H(4A)
H(6A)
H(7A)
H(8A)
H(8B)
63
67
67
H(9A)
H(10A)
H(10B)
H(11A)
H(13A)
H(13B)
H(13C)
H(14A)
H(14B)
H(14C)
69
96
96
158
295
295
295
435
435
435
________________________________________________________________________________

Supporting Information
S27
ORTEP of 31
O
O
S
HN
O
AcO
31

Supporting Information
S28
Table 1. Crystal data and structure refinement for 31.
Identification code
Empirical formula
Formula weight
Temperature
1542_0m
C6 H11 N O5 S
209.22
296(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P 1 21/c 1
Unit cell dimensions
a = 9.4821(2) Å
b = 7.4935(2) Å
c = 12.6861(3) Å
899.53(4) Å3
4
ꢀ= 90°.
ꢀ= 93.6860(10)°.
ꢀ = 90°.
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
1.545 Mg/m3
0.351 mm-1
440
Crystal size
0.20 x 0.20 x 0.20 mm3
2.15 to 28.29°.
Theta range for data collection
Index ranges
-12<=h<=12, -9<=k<=9, -16<=l<=16
8235
Reflections collected
Independent reflections
Completeness to theta = 28.29°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
2222 [R(int) = 0.0187]
99.6 %
Semi-empirical from equivalents
0.9331 and 0.9331
Full-matrix least-squares on F2
2222 / 0 / 122
1.065
R1 = 0.0500, wR2 = 0.1464
R1 = 0.0595, wR2 = 0.1575
0.610 and -0.678 e.Å-3

Supporting Information
S29
4
2
3
Table 2. Atomic coordinates ( x 10 ) and equivalent isotropic displacement parameters (Å x 10 )
ij
for 31. U(eq) is defined as one third of the trace of the orthogonalized U tensor.
_
_______________________________________________________________________________
U(eq)
_______________________________________________________________________________
x
y
z
_
S(1)
N(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
O(1)
O(2)
O(3)
O(4)
O(5)
3000(1)
3104(2)
1852(3)
1444(2)
906(3)
1397(1)
3521(3)
4652(4)
5172(3)
3676(3)
2061(3)
7193(3)
7719(5)
801(3)
7202(1)
7105(2)
7075(2)
8169(2)
8823(2)
8962(2)
9417(2)
9925(3)
7621(2)
6240(2)
7973(2)
8691(2)
9622(2)
36(1)
38(1)
43(1)
36(1)
38(1)
40(1)
41(1)
61(1)
63(1)
61(1)
43(1)
42(1)
51(1)
1833(3)
2578(3)
3980(3)
4336(2)
2428(2)
1811(2)
2721(2)
1453(2)
633(3)
1054(2)
5911(2)
7805(2)
________________________________________________________________________________