Generation and Ring Opening of Aziridines in Telescoped Continuous Flow Processes.
Hsueh, Nathanael; Clarkson, Guy J.; Shipman, Michael; Organic letters 17 (2015) 3632–3635; doi:10.1021/acs.orglett.5b01777

data_1555114
_publ_section_title
;
 Generation and Ring Opening of Aziridines in Telescoped Continuous Flow
 Processes.
;
_journal_issue                   14
_journal_name_full               'Organic letters'
_journal_page_first              3632
_journal_page_last               3635
_journal_paper_doi               10.1021/acs.orglett.5b01777
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H23 N O5 S'
_chemical_formula_sum            'C18 H23 N O5 S'
_chemical_formula_weight         365.43
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                82.659(3)
_cell_angle_beta                 70.506(3)
_cell_angle_gamma                68.236(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6291(3)
_cell_length_b                   9.4332(3)
_cell_length_c                   12.4474(4)
_cell_measurement_reflns_used    5710
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      78.2660
_cell_measurement_theta_min      3.7510
_cell_volume                     887.04(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega   18.00   47.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000    0.0000 -180.0000 29

  2 omega  -50.00   24.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000 -150.0000 74

  3 omega -112.00   14.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000    0.0000 -180.0000 126

  4 omega   31.00   90.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3790 -125.0000   90.0000 59

  5 omega   33.00   96.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       43.3790 -125.0000  -30.0000 63

  6 omega   41.00   72.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000   30.0000 31

  7 omega   93.00  155.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   45.0000  -90.0000 62

  8 omega   71.00  114.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000  120.0000 43

  9 omega   46.00   84.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -77.0000 -180.0000 38

 10 omega   46.00   97.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000   30.0000 51

 11 omega  108.00  134.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -77.0000 -180.0000 26

 12 omega   76.00  112.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000  -30.0000 36

 13 omega   44.00  113.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000    0.0000  -90.0000 69

 14 omega  125.00  159.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000    0.0000  -90.0000 34

 15 omega   42.00   85.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000   90.0000 43

 16 omega  110.00  173.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  111.0000 -180.0000 63

 17 omega   47.00   96.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000 -120.0000 49

 18 omega   35.00  106.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -94.0000   30.0000 71

 19 omega   45.00   83.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000  -90.0000 38

 20 omega   94.00  172.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000   30.0000  120.0000 78

 21 omega   55.00  104.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -94.0000 -120.0000 49

 22 omega   42.00   68.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000 -150.0000 26

 23 omega   83.00  116.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000 -150.0000 33

 24 omega   43.00   69.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000  -30.0000 26

 25 omega   91.00  116.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000   30.0000 25

 26 omega   65.00   93.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  178.0000 -120.0000 28

 27 omega  105.00  144.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  178.0000 -120.0000 39

 28 omega   47.00   91.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000  150.0000 44
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0690919000
_diffrn_orient_matrix_UB_12      0.1306631000
_diffrn_orient_matrix_UB_13      -0.0788074000
_diffrn_orient_matrix_UB_21      -0.1900828000
_diffrn_orient_matrix_UB_22      0.0173039000
_diffrn_orient_matrix_UB_23      0.0714936000
_diffrn_orient_matrix_UB_31      -0.0014302000
_diffrn_orient_matrix_UB_32      0.1164071000
_diffrn_orient_matrix_UB_33      0.0769164000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7775
_diffrn_reflns_point_group_measured_fraction_full 0.594
_diffrn_reflns_point_group_measured_fraction_max 0.580
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.970
_diffrn_reflns_theta_min         3.767
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.871
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57388
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description       block
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.755
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.

Hooft y: 0.02(2)  Olex2
Flack x: 0.009(18)  Shelx 2014
;
_refine_ls_abs_structure_Flack   0.009(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     465
_refine_ls_number_reflns         4416
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0706P)^2^+0.2408P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1167
_reflns_Friedel_coverage         0.175
_reflns_Friedel_fraction_full    0.189
_reflns_Friedel_fraction_max     0.173
_reflns_number_gt                4347
_reflns_number_total             4416
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b01777_si_002.cif
_cod_data_source_block           nh2
_cod_database_code               1555114
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C20 H20 N2 O2 S'
_reflns_odcompleteness_completeness 97.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.89
_olex2_refinement_description
;

There are B alerts in the cifchecker for pseudo centre of symmmetry.
Attempted refinement in P-1 resulted in very large thermal parameters
and unusual bond angles and a high Rint(19%)
The refinement in space group P1 gives two S enantiomers in the unit cell
with low Flack and Hooft parameters (with low error and reasonable thermal parameters.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C205(H205), C105(H105)
2.b Secondary CH2 refined with riding coordinates:
 C204(H20D,H20E), C104(H10D,H10E)
2.c Aromatic/amide H refined with riding coordinates:
 C00U(H00U), C207(H207), C208(H208), C209(H209), C210(H210), C213(H213),
 C215(H215), C107(H107), C108(H108), C109(H109), C110(H110), C111(H111),
 C114(H114), C116(H116)
2.d Idealised Me refined as rotating group:
 C201(H20A,H20B,H20C), C218(H21A,H21B,H21C), C220(H22A,H22B,H22C), C222(H22D,
 H22E,H22F), C101(H10A,H10B,H10C), C119(H11A,H11B,H11C), C121(H12A,H12B,H12C),
 C123(H12D,H12E,H12F)
;
_olex2_submission_special_instructions 'No special instructions were received'