Synthesis of cyclic hydroxamic acids through -NOH insertion of ketones

Article abstract of DOI:10.1021/ol9018198

Treatment of cyclobutanone or cyclopentanone with N- hydroxybenzenesulfonamide under basic conditions yields the ring-expanded cyclic hydroxamic acid in 18-69% yield. Reactions of substituted cyclobutanones give ring expanded products where the -NOH group regio- and stereoselectively inserts to the more substituted position. This expansion likely proceeds through a mechanism that includes addition of the N-anion of N-hydroxybenzenesulfonamide to the ketone and a C-nitroso intermediate that rearranges to the final product.

Full text of DOI:10.1021/ol9018198

X-Ray Reports for
Synthesis of Cyclic Hydroxamic Acids Through –NOH Insertion of
Ketones
Ranjan Banerjee and S. Bruce King
Department of Chemistry, Wake Forest University, Winston-Salem, NC 27109
kingsb@wfu.edu
Supporting Information
1. Report for 1
2. Report for 4
S2
S13
S1

X-Ray Report for 1
O
OH
N
1
The asymmetric unit contains two C5H9NO2 molecules. One of the C5H9NO2 molecules shows
minor disorder involving two of the ring carbon atoms. All displacement ellipsoids are drawn at
the 50% probability level.
Colorless rectangular-parallelepiped-shaped crystals of C5H9NO2 are, at 193(2) K,
orthorhombic, space group Pbca – D15 (No. 61)1 with a = 15.900(3) Å, b = 7.187(1) Å, c =
2h
19.995(4) Å, V = 2284.9(8) Å3 and Z = 16 molecules {dcalcd = 1.339 g/cm3; ꢀa(MoKα ) = .103
mm-1}. A full hemisphere of diffracted intensities (1868 20-second frames with a ω scan width
of 0.30°) was measured for a single-domain specimen using graphite-monochromated MoKα
radiation (λ= 0.71073 Å) on a Bruker SMART APEX CCD Single Crystal Diffraction System.2
X-rays were provided by a fine-focus sealed x-ray tube operated at 50kV and 30mA. Lattice
constants were determined with the Bruker SAINT software package using peak centers for 5101
reflections. A total of 21446 integrated reflection intensities having 2θ((MoKα )< 58.70° were
produced using the Bruker program SAINT;3 3116 of these were unique and gave Rint = 0.058
with a coverage which was 99.6% complete. The relative transmission factors ranged from
0.966 to 0.990. The Bruker software package SHELXTL was used to solve the structure using
“direct methods” techniques. All stages of weighted full-matrix least-squares refinement were
2
conducted using Fo data with the SHELXTL Version 6.12 software package.4
The final structural model incorporated anisotropic thermal parameters for all
nonhydrogen atoms and isotropic thermal parameters for all hydrogen atoms. Hydroxyl
hydrogen atoms were located from a difference Fourier map and refined as independent
isotropic atoms. The remaining hydrogen atoms were included into the structural model
as idealized atoms (assuming sp3-hybridization of the carbon atoms and C-H bond
lengths of 0.99 Å). The isotropic thermal parameters for H2O and H4O refined to final
values of 0.069(5) and 0.066(5)Å2, respectively. The isotropic thermal parameters of the
remaining hydrogen atoms were fixed at values 1.2 times the equivalent isotropic thermal
parameter of the carbon atom to which they are covalently bonded.
One of the two independent molecules shows disorder involving two of the ring
carbon atoms with two orientations in the crystal; the major orientation is adopted 71 %
of the time and the minor orientation is adopted 29 % of the time. The major (71%)
orientation is specified by carbon atoms C8 and C9 and hydrogen atoms H7A, H7B, H8A,
H8B, H9A, H9B, H10A and H10B; the minor (29%) orientation is specified by carbon atoms
C8’ and C9’ and hydrogen atoms H7C, H7D, H8’A, H8’B, H9’A, H9’B, H10C and H10D
,
respectively.
A total of 172 parameters were refined using no restraints, 3116 data and weights
2 2
2
2
2
of w = 1/ [σ (F ) + (0.0816 P) ], where P = [F + 2F ] / 3. Final agreement factors at
o
c
convergence are: R1(unweighted, based on F) = 0.048 for 2332 independent “observed”
S2

reflections having 2θ(MoKα )< 58.70° and I>2σ(I); R1(unweighted, based on F) =
0.062 and wR2(weighted, based on F2) = 0.130 for all 3116 independent reflections
having 2θ(MoKα )< 58.70°. The largest shift/s.u. was 0.000 in the final refinement cycle.
-
3
The final difference map had maxima and minima of 0.30 and -0.16 e /Å , respectively.
References
(1) International Tables for Crystallography, Vol A, 4th ed., Kluwer: Boston (1996).
(2) Data Collection: SMART Software Version 5.628 (2002). Bruker-AXS, 5465 E. Cheryl
Parkway, Madison, WI 53711-5373 USA.
(3) Data Reduction: SAINT Software Version 6.36a (2002). Bruker-AXS, 5465 E. Cheryl
Parkway, Madison, WI 53711-5373 USA.
(4) G. M. Sheldrick (2000). SHELXTL Version 6.12 Reference Manual. Bruker-AXS, 5465 E.
Cheryl Parkway, Madison, WI 53711-5373 USA
S3

Table 1. Crystal data and structure refinement for C5H9NO2
Identification code
Empirical formula
Formula weight
Temperature
a52m2m
C5 H9 N O2
115.13
193(2) K
0.71073 Å
Wavelength
Crystal system
Space group
Orthorhombic
15
Pbca – D
(No. 61)
2h
Unit cell dimensions
a = 15.900(3) Å
b = 7.187(1) Å
c = 19.995(4) Å
3
Volume
2284.9(8) Å
16
Z
3
Density (calculated)
Absorption coefficient
F(000)
1.339 g/cm
-1
0.103 mm
992
3
Crystal size
0.34 x 0.13 x 0.10 mm
3.82 to 29.35°
Theta range for data collection
Index ranges
-20≤h≤21, -9≤k≤9, -27≤l≤27
21446
Reflections collected
Independent reflections
Completeness to theta = 29.35°
Absorption correction
Max. and min. transmission
Refinement method
Data / parameters
3116 [R(int) = 0.0576]
99.6 %
None
0.9897 and 0.9657
Full-matrix least-squares on F
3116 / 172
2
2
Goodness-of-fit on F
0.980
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0478, wR2 = 0.1214
R1 = 0.0620, wR2 = 0.1295
- 3
Largest diff. peak and hole
0.304 and -0.165 e /Å
------------------------------------------------------------------------------------------------------------------------
R1 = Σ ||F | - |F || / Σ |F |
o
c
o
2
2 2
2 2 1/2
wR2 = { Σ [w(F - F ) ] / Σ [w(F ) ] }
o
c
o
S4

4
2
Table 2. Atomic coordinates (x 10 ) and equivalent isotropic displacement parameters (Å x
3
ij
10 ) for C5H9NO2. U(eq) is defined as one third of the trace of the orthogonalized U tensor.
______________________________________________________________________________
x
y
z
U(eq)
______________________________________________________________________________
O(1)
O(2)
N(1)
C(1)
C(2)
C(3)
C(4)
C(5)
O(3)
O(4)
N(2)
C(6)
C(7)
C(8)
C(9)
C(10)
C(8')
C(9')
771(1)
1634(1)
1448(1)
1045(1)
1867(1)
1534(1)
1473(1)
899(1)
-1432(1)
441(1)
1876(1)
958(1)
1583(1)
2020(1)
1714(1)
2342(1)
2905(1)
2704(1)
69(1)
51(1)
42(1)
32(1)
33(1)
45(1)
58(1)
50(1)
44(1)
38(1)
45(1)
36(1)
31(1)
47(1)
50(1)
45(1)
38(1)
40(1)
41(1)
1205(1)
131(2)
2964(2)
3864(2)
2487(2)
926(2)
656(1)
1986(1)
3562(1)
3080(1)
2329(2)
3599(2)
3574(3)
1853(4)
1901(2)
2496(7)
2866(10)
-278(1)
-609(1)
-95(1)
-876(1)
-254(1)
193(1)
-171(1)
593(1)
925(1)
872(1)
316(2)
928(3)
-1490(1)
-1727(1)
-1378(1)
-458(1)
-1920(3)
-1411(3)
______________________________________________________________________________
S5

Table 3. Bond lengths [Å] and angles [°] for C5H9NO2
_______________________________________________________________________
O(1)-C(1)
O(2)-N(1)
O(2)-H(2O)
1.239(1)
1.397(1)
0.88(2)
O(3)-C(6)
O(4)-N(2)
O(4)-H(4O)
1.245(1)
1.394(1)
0.87(2)
N(1)-C(1)
N(1)-C(2)
1.329(2)
1.453(2)
N(2)-C(6)
N(2)-C(7)
1.325(2)
1.459(2)
C(1)-C(5)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
1.501(2)
1.508(2)
1.501(2)
1.502(2)
C(6)-C(10)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
1.506(2)
1.572(3)
1.510(3)
1.467(3)
C(7)-C(8')
C(8')-C(9')
1.430(5)
1.492(7)
C(10)-C(9')
1.670(6)
N(1)-O(2)-H(2O)
106.4(12)
N(2)-O(4)-H(4O)
105.7(12)
C(1)-N(1)-O(2)
C(1)-N(1)-C(2)
O(2)-N(1)-C(2)
117.46(10)
127.41(10)
113.98(9)
C(6)-N(2)-O(4)
C(6)-N(2)-C(7)
O(4)-N(2)-C(7)
118.00(10)
128.25(11)
113.62(10)
O(1)-C(1)-N(1)
O(1)-C(1)-C(5)
N(1)-C(1)-C(5)
N(1)-C(2)-C(3)
C(4)-C(3)-C(2)
C(3)-C(4)-C(5)
C(1)-C(5)-C(4)
122.96(11)
120.10(11)
116.90(10)
111.24(11)
111.34(13)
109.32(12)
115.72(11)
O(3)-C(6)-N(2)
O(3)-C(6)-C(10)
N(2)-C(6)-C(10)
N(2)-C(7)-C(8)
C(9)-C(8)-C(7)
C(10)-C(9)-C(8)
C(9)-C(10)-C(6)
122.47(11)
120.49(11)
117.04(11)
109.75(12)
110.38(18)
108.4(2)
116.85(13)
C(8')-C(7)-N(2)
C(7)-C(8')-C(9')
113.3(2)
101.5(4)
C(8')-C(9')-C(10)
C(6)-C(10)-C(9')
111.3(4)
108.9(2)
S6

2
3
Table 4. Anisotropic displacement parameters (Å x 10 ) for C5H9NO2. The anisotropic
2 11 12
2
2
displacement factor exponent takes the form: -2π [ h a* U + ... + 2 h k a* b* U
______________________________________________________________________________
11 22 33 23 13 12
]
U
U
U
U
U
U
______________________________________________________________________________
O(1)
O(2)
N(1)
C(1)
C(2)
C(3)
C(4)
C(5)
O(3)
O(4)
N(2)
C(6)
C(7)
C(8)
C(9)
C(10)
C(8')
C(9')
70(1)
40(1)
31(1)
33(1)
47(1)
70(1)
54(1)
55(1)
36(1)
63(1)
42(1)
37(1)
42(1)
43(1)
37(1)
42(1)
33(2)
36(3)
38(1)
55(1)
36(1)
31(1)
38(1)
36(1)
53(1)
42(1)
42(1)
41(1)
33(1)
24(1)
41(1)
54(1)
49(1)
39(1)
44(3)
43(3)
46(1)
30(1)
29(1)
35(1)
49(1)
69(1)
43(1)
36(1)
35(1)
31(1)
33(1)
31(1)
59(1)
53(1)
49(1)
31(1)
45(3)
44(3)
-6(1)
0(1)
5(1)
3(1)
1(1)
0(1)
1(1)
3(1)
0(1)
9(1)
2(1)
-4(1)
-2(1)
-2(1)
-10(1)
1(1)
5(1)
2(1)
-3(2)
7(2)
-18(1)
10(1)
-1(1)
-2(1)
-11(1)
-11(1)
-6(1)
-8(1)
1(1)
1(1)
1(1)
8(1)
-9(1)
-14(1)
-4(1)
-1(1)
5(1)
-11(1)
-1(1)
-3(1)
8(1)
2(1)
-5(1)
3(1)
4(1)
19(1)
7(1)
10(1)
-1(1)
-8(2)
0(3)
1(1)
-2(2)
9(3)
______________________________________________________________________________
S7

4
2
3
Table 5. Hydrogen coordinates (x 10 ) and isotropic displacement parameters (Å x 10 )
for C5H9NO2.
______________________________________________________________________________
x
y
z
U(eq)
______________________________________________________________________________
H(2O)
H(2A)
H(2B)
H(3A)
H(3B)
H(4A)
H(4B)
H(5A)
H(5B)
H(4O)
H(7A)
H(7B)
H(7C)
H(7D)
H(8A)
H(8B)
H(9A)
H(9B)
H(10A)
H(10B)
H(10C)
H(10D)
H(8'A)
H(8'B)
H(9'A)
H(9'B)
1288(12)
1780
2479
1911
971
970(30)
3812
672(9)
1331
1762
2475
2252
3310
3010
3035
2727
-1152(8)
-418
-356
-36
69(5)
54
54
70
70
60
60
53
53
66(5)
57
57
57
57
60
60
54
54
45
45
45
45
48
48
49
49
2747
4895
4394
3109
1990
-90
1251
2038
957
311
1379
2720(30)
2714
4859
4923
3471
4697
3596
1820
724
-458(11)
-1852
-1585
-1521
-1780
-1497
-2347
-1548
-1600
-238
-606
814
642
1401
703
677
1017
1191
1226
934
-245
2843
2405
537
-87
-501
-1912
-2510
-1707
-1351
1160
2908
2359
4226
196
373
1324
991
________________________________________________________________________
S8

Table 6. Torsion angles [°] for C5H9NO2
________________________________________________________________
O(2)-N(1)-C(1)-O(1)
C(2)-N(1)-C(1)-O(1)
O(2)-N(1)-C(1)-C(5)
C(2)-N(1)-C(1)-C(5)
C(1)-N(1)-C(2)-C(3)
O(2)-N(1)-C(2)-C(3)
N(1)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-C(5)
O(1)-C(1)-C(5)-C(4)
N(1)-C(1)-C(5)-C(4)
C(3)-C(4)-C(5)-C(1)
O(4)-N(2)-C(6)-O(3)
C(7)-N(2)-C(6)-O(3)
O(4)-N(2)-C(6)-C(10)
C(7)-N(2)-C(6)-C(10)
C(6)-N(2)-C(7)-C(8')
O(4)-N(2)-C(7)-C(8')
C(6)-N(2)-C(7)-C(8)
O(4)-N(2)-C(7)-C(8)
N(2)-C(7)-C(8)-C(9)
C(7)-C(8)-C(9)-C(10)
C(8)-C(9)-C(10)-C(6)
O(3)-C(6)-C(10)-C(9)
N(2)-C(6)-C(10)-C(9)
O(3)-C(6)-C(10)-C(9')
N(2)-C(6)-C(10)-C(9')
N(2)-C(7)-C(8')-C(9')
C(7)-C(8')-C(9')-C(10)
C(6)-C(10)-C(9')-C(8')
-6.27(17)
-173.16(12)
176.17(10)
9.27(18)
-22.01(18)
170.71(11)
46.37(17)
-59.18(17)
160.80(13)
-21.57(18)
46.40(18)
-2.47(16)
-178.17(12)
177.28(9)
1.58(18)
-28.4(3)
155.8(2)
13.0(2)
-162.85(13)
-44.4(2)
61.8(3)
-48.1(3)
-163.59(17)
16.7(2)
169.6(3)
-10.1(3)
59.2(4)
-69.3(5)
46.0(5)
________________________________________________________________
S9

Table 7. Hydrogen bonds for C5H9NO2 [Å and °]
____________________________________________________________________________
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
____________________________________________________________________________
O(2)-H(2O)...O(3)
0.88(2)
1.73(2)
2.6101(13)
2.6383(14)
176.3(18)
165.4(18)
O(4)-H(4O)...O(1)#1 0.868(18)
1.789(18)
____________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x,-y,-z
S10

S11

S12

X-Ray Report for 4
Crystals of C7H11NO2 contain two crystallographically-independent molecules per
asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level in
thermal ellipsoid plots.
S13

Table 1. Crystal data and structure refinement for C7H11NO2
Identification code
Empirical formula
Formula weight
Temperature
a11m
C7 H11 N O2
141.17
193(2) K
0.71073 Å
Wavelength
Crystal system
Space group
Monoclinic
P2(1)/c - C52h (No. 14)
Unit cell dimensions
a = 13.040(3) Å
b = 10.086(3) Å, β = 92.336(3)°
c = 10.802(3) Å
3
Volume
1419.5(6) Å
Z
8
3
Density (calculated)
Absorption coefficient
F(000)
1.321 g/cm
-1
0.097 mm
608
3
Crystal size
0.18 x 0.12 x 0.08 mm
4.03 to 25.00°
Theta range for data collection
Index ranges
-15≤h≤15, 0≤k≤11, 0≤l≤12
3820
Reflections collected
Independent reflections
Completeness to theta = 25.00°
Refinement method
Data / parameters
3822 [R(int) = 0.0000]
99.6 %
2
Full-matrix least-squares on F
3822 / 190
2
Goodness-of-fit on F
1.194
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0684, wR2 = 0.1301
R1 = 0.0845, wR2 = 0.1365
- 3
Largest diff. peak and hole
0.213 and -0.172 e /Å
------------------------------------------------------------------------------------------------------------------------
R1 = Σ ||F | - |F || / Σ |F |
o
c
o
2
2 2
2 2 1/2
wR2 = { Σ [w(F - F ) ] / Σ [w(F ) ] }
o
c
o
S14

a,b
Table 3. Bond lengths [Å] and angles [°] for C7H11NO2
__________________________________________________________________________
O(1A)-N(1A)
O(1A)-H(1A)
O(2A)-C(1A)
N(1A)-C(1A)
N(1A)-C(2A)
C(1A)-C(4A)
1.387(2)
0.94(2)
O(1B)-N(1B)
O(1B)-H(1B)
O(2B)-C(1B)
N(1B)-C(1B)
N(1B)-C(2B)
C(1B)-C(4B)
1.383(2)
0.90(3)
1.237(2)
1.327(3)
1.454(3)
1.495(3)
1.230(3)
1.321(3)
1.456(3)
1.496(3)
C(2A)-C(5A)
C(2A)-C(3A)
C(3A)-C(7A)
C(3A)-C(4A)
C(5A)-C(6A)
C(6A)-C(7A)
1.519(3)
1.549(3)
1.524(3)
1.528(3)
1.518(3)
1.519(3)
C(2B)-C(5B)
C(2B)-C(3B)
C(3B)-C(7B)
C(3B)-C(4B)
C(5B)-C(6B)
C(6B)-C(7B)
1.520(3)
1.553(3)
1.520(3)
1.529(3)
1.518(4)
1.506(4)
N(1A)-O(1A)-H(1A)
105.1(14)
N(1B)-O(1B)-H(1B)
104.9(18)
C(1A)-N(1A)-O(1A)
C(1A)-N(1A)-C(2A)
O(1A)-N(1A)-C(2A)
121.53(18)
117.47(17)
119.07(16)
C(1B)-N(1B)-O(1B)
C(1B)-N(1B)-C(2B)
O(1B)-N(1B)-C(2B)
121.56(17)
117.72(18)
120.34(18)
O(2A)-C(1A)-N(1A)
O(2A)-C(1A)-C(4A)
N(1A)-C(1A)-C(4A)
125.3(2)
127.2(2)
107.48(18)
O(2B)-C(1B)-N(1B)
O(2B)-C(1B)-C(4B)
N(1B)-C(1B)-C(4B)
126.4(2)
126.2(2)
107.37(19
S15

N(1A)-C(2A)-C(5A)
N(1A)-C(2A)-C(3A)
C(5A)-C(2A)-C(3A)
C(7A)-C(3A)-C(4A)
N(1B)-C(2B)-C(5B)
N(1B)-C(2B)-C(3B)
C(5B)-C(2B)-C(3B)
C(7B)-C(3B)-C(4B)
C(7A)-C(3A)-C(2A)
C(4A)-C(3A)-C(2A)
111.66(18)
102.36(17)
106.47(18)
114.47(19)
112.04(19)
102.35(18)
105.7(2)
C(1A)-C(4A)-C(3A)
C(6A)-C(5A)-C(2A)
C(5A)-C(6A)-C(7A)
C(6A)-C(7A)-C(3A)
C(7B)-C(3B)-C(2B)
C(4B)-C(3B)-C(2B)
C(1B)-C(4B)-C(3B)
C(6B)-C(5B)-C(2B)
C(7B)-C(6B)-C(5B)
C(6B)-C(7B)-C(3B)
106.69(18)
103.55(19)
102.39(19)
104.17(19)
104.7(2)
105.41(17)
106.87(19)
104.6(2)
113.6(2)
104.70(18)
105.73(17)
102.0(2)
104.6(2)
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a
The numbers in parentheses are the estimated standard deviations in the last
significant digit.
Atoms are labeled in agreement with Figures 1 and 2.
b
S16

Table 7. Inter-molecular Hydrogen bonds for C7H11NO2 [Å and °]
________________________________________________________________________
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
________________________________________________________________________
O(1A)-H(1A)...O(2B)#1 0.94(2)
O(1B)-H(1B)...O(2A) 0.90(3)
1.71(3)
1.69(3)
2.648(2)
2.584(2)
178(2)
173(3)
________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,y+1/2,-z+1/2
S17

S18

S19