An Organophotocatalytic Late-stage N-CH3 Oxidation of Trialkylamines to N-formamides with O2 in Continuous Flow
Mandigma, Mark John; Zurauskas, Jonas; MacGregor, Callum Ian; Edwards, Lee; Shahin, Ahmed; d'Heureuse, Ludwig; Yip, Philip; Birch, David J. S.; Gruber, Thomas; Heilmann, Jorg; John, Matthew P.; Barham, Joshua Philip; Chemical Science  (2022) –; doi:10.1039/D1SC05840A

data_1565844
_publ_section_title
;
 An Organophotocatalytic Late-stage N-CH3 Oxidation of Trialkylamines to
 N-formamides with O2 in Continuous Flow
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC05840A
_journal_year                    2022
_chemical_formula_moiety         'C28 H34 N4 O8 S2'
_chemical_formula_sum            'C28 H34 N4 O8 S2'
_chemical_formula_weight         618.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-08-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-13 deposited with the CCDC.	2021-12-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.317(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.7306(7)
_cell_length_b                   5.04920(10)
_cell_length_c                   24.8887(5)
_cell_measurement_reflns_used    11432
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      72.4530
_cell_measurement_theta_min      3.7110
_cell_volume                     2984.57(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution
'olex2.solve 1.3-alpha (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     27.00  71.84   0.38    0.40    --   62.55-104.00 109.00  118
  2  \w     38.00  82.84   0.38    1.60    --   73.48-104.00 109.00  118
  3  \w     36.00 101.74   0.38    0.40    --   62.55  15.00  60.00  173
  4  \w     36.00 101.74   0.38    0.40    --   62.55  15.00 -90.00  173
  5  \w     24.00  84.80   0.38    0.40    --   62.55-125.00-150.00  160
  6  \w     36.00 101.74   0.38    0.40    --   62.55  15.00   0.00  173
  7  \w     36.00 101.74   0.38    0.40    --   62.55  15.00-150.00  173
  8  \w     24.00  84.80   0.38    0.40    --   62.55-125.00-120.00  160
  9  \w     36.00 101.74   0.38    0.40    --   62.55  15.00 120.00  173
 10  \w     24.00  84.80   0.38    0.40    --   62.55-125.00 -90.00  160
 11  \w    -88.00 -26.06   0.38    0.40    --  -64.35 125.00  90.00  163
 12  \w   -105.00 -39.26   0.38    0.40    --  -64.35 -15.00  30.00  173
 13  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00-180.00  163
 14  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00-120.00  163
 15  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00  60.00  163
 16  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00 120.00  163
 17  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00 -60.00  163
 18  \w   -109.00 -43.26   0.38    0.40    --  -68.39 -15.00 -30.00  173
 19  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00   0.00  163
 20  \w    -92.00 -30.06   0.38    0.40    --  -68.39 125.00 -30.00  163
 21  \w     47.00 112.74   0.38    1.60    --   73.48  15.00 150.00  173
 22  \w     47.00 112.74   0.38    1.60    --   73.48  15.00-150.00  173
 23  \w     35.00  95.80   0.38    1.60    --   73.48-125.00 120.00  160
 24  \w     35.00  95.80   0.38    1.60    --   73.48-125.00-120.00  160
 25  \w     47.00 112.74   0.38    1.60    --   73.48  15.00 -90.00  173
 26  \w     49.00 114.74   0.38    1.60    --   75.18  15.00   0.00  173
 27  \w     36.00  97.94   0.38    1.60    --   75.18-125.00 150.00  163
 28  \w     36.00  97.94   0.38    1.60    --   75.18-125.00  60.00  163
 29  \w     36.00  97.94   0.38    1.60    --   75.18-125.00 -90.00  163
 30  \w     36.00  97.94   0.38    1.60    --   75.18-125.00   0.00  163
 31  \w     49.00 114.74   0.38    1.60    --   75.18  15.00  30.00  173
 32  \w     36.00  97.94   0.38    1.60    --   75.18-125.00 -30.00  163
 33  \w     36.00  97.94   0.38    1.60    --   75.18-125.00-150.00  163
 34  \w     72.00  98.22   0.38    1.60    --   75.18-125.00  30.00   69
 35  \w     37.00  80.32   0.38    1.60    --   75.18-125.00-180.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0178208000
_diffrn_orient_matrix_UB_12      -0.2762368000
_diffrn_orient_matrix_UB_13      -0.0112849000
_diffrn_orient_matrix_UB_21      0.0607361000
_diffrn_orient_matrix_UB_22      0.1002423000
_diffrn_orient_matrix_UB_23      0.0222453000
_diffrn_orient_matrix_UB_31      0.0143490000
_diffrn_orient_matrix_UB_32      -0.0822389000
_diffrn_orient_matrix_UB_33      0.0650725000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25114
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.171
_diffrn_reflns_theta_min         3.722
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.091
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.858
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       needle
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.095
_exptl_crystal_size_mid          0.046
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.811
_refine_diff_density_min         -0.393
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         2930
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0448
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0581P)^2^+8.1463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1216
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2584
_reflns_number_total             2930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05840a2.cif
_cod_data_source_block           u089_pl
_cod_database_code               1565844
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H34 N4 O8 S2'
_chemical_oxdiff_usercomment     Zurauskas_Barham_1
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.826
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13A-C12 \\sim C13-C12
 with sigma of 0.02
 O4A-C13A \\sim O4-C13
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 O4A-C14A \\sim O4-C14
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C14 \\sim C14A \\sim O4 \\sim O4A: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.005 within 1.7A
C13A \\sim C13: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.005 within 1.7A
4. Others
 Sof(H12C)=Sof(H12D)=Sof(O4A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=1-FVAR(1)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H12A)=Sof(H12B)=Sof(O4)=Sof(C14)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C10(H10A,H10B), C9(H9A,H9B), C12(H12A,H12B), C12(H12C,H12D),
 C13A(H13C,H13D)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7)
5.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              83932
_shelx_hkl_checksum              33147
_olex2_date_sample_data_collection 2021-08-09
_olex2_date_sample_submission    2021-08-03
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems CryoStream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with inert oil'
_olex2_submission_original_sample_id 1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.900
_oxdiff_exptl_absorpt_empirical_full_min 0.687