Catalyst- and solvent-free regioselective ring opening of aziridines with amines: application in the gram-scale synthesis of the α,β-diamino propionic derivative, aspergillomarasmine A.
Lin, Xing; Zhang, Dajun; Li, Jing; Zhang, Lei; Organic & biomolecular chemistry 21 (2023) 4977–4981; doi:10.1039/d3ob00722g

data_7159391
_publ_section_title
;
 Catalyst- and solvent-free regioselective ring opening of aziridines with
 amines: application in the gram-scale synthesis of the
 &#x3b1;,&#x3b2;-diamino propionic derivative, aspergillomarasmine A.
;
_journal_issue                   24
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4977
_journal_page_last               4981
_journal_paper_doi               10.1039/d3ob00722g
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H21 N3 O6 S'
_chemical_formula_sum            'C22 H21 N3 O6 S'
_chemical_formula_weight         455.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_audit_update_record
;
2023-03-13 deposited with the CCDC.	2023-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.58560(10)
_cell_length_b                   12.11150(10)
_cell_length_c                   21.14980(10)
_cell_measurement_reflns_used    17414
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6090
_cell_measurement_theta_min      3.6350
_cell_volume                     2199.25(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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     33.00 105.00   0.50    0.05    --  111.82 -96.00 127.00  144
  2  \w     71.00 103.00   0.50    0.05    --  111.82-111.00   0.00   64
  3  \w     37.00  62.00   0.50    0.05    --  111.82-111.00   0.00   50
  4  \w     33.00  79.00   0.50    0.05    --  111.82 -94.00-180.00   92
  5  \w     42.00  67.00   0.50    0.05    --  111.82 -61.00-150.00   50
  6  \w     64.00  99.00   0.50    0.05    --  111.82 -76.00-136.00   70
  7  \w     60.00 101.00   0.50    0.05    --  111.82 -77.00 -60.00   82
  8  \w     40.00  66.00   0.50    0.05    --  111.82 -61.00 -90.00   52
  9  \w     39.00  67.00   0.50    0.05    --  111.82 -61.00 -60.00   56
 10  \w     40.00  66.00   0.50    0.05    --  111.82 -61.00-180.00   52
 11  \w     65.00  91.00   0.50    0.05    --  111.82 -77.00  60.00   52
 12  \w     39.00  65.00   0.50    0.05    --  111.82 -61.00 120.00   52
 13  \w    105.00 131.00   0.50    0.05    --  111.82 179.00-120.00   52
 14  \w     78.00 104.00   0.50    0.05    --  111.82 179.00-120.00   52
 15  \w     90.00 116.00   0.50    0.05    --  111.82  76.00  -9.00   52
 16  \w    124.00 156.00   0.50    0.05    --  111.82  45.00 -90.00   64
 17  \w    150.00 175.00   0.50    0.05    --  111.82  76.00  -9.00   50
 18  \w     84.00 171.00   0.50    0.05    --  111.82  45.00 -60.00  174
 19  \w     95.00 121.00   0.50    0.05    --  111.82  45.00 -90.00   52
 20  \w    140.00 175.00   0.50    0.05    --  111.82  54.00 138.00   70
 21  \w     90.00 126.00   0.50    0.05    --  111.82  54.00 138.00   72
 22  \w     14.00 116.00   0.50    0.05    --   39.45  54.00 138.00  204
 23  \w    -74.00  27.00   0.50    0.05    --  -39.45  76.00  -9.00  202
 24  \w    -38.00  14.00   0.50    0.05    --  -39.45  96.00-123.00  104
 25  \w   -131.00 -92.00   0.50    0.05    --  -52.00 -94.00  90.00   78
 26  \w     45.00  70.00   0.50    0.05    --  111.82 -96.00 127.00   50
 27  \w     71.00  97.00   0.50    0.05    --  111.82 -77.00  90.00   52
 28  \w    -79.00 -53.00   0.50    0.05    --  -39.45 -54.00  -5.00   52
 29  \w    -39.00 -13.00   0.50    0.05    --  -39.45 -54.00  -5.00   52
 30  \w    -27.00   0.00   0.50    0.05    --   39.45 -19.00   0.00   54
 31  \w    -25.00  29.00   0.50    0.05    --  -52.00  15.00 120.00  108
 32  \w    -55.00 -23.00   0.50    0.05    --  -52.00 -61.00-120.00   64
 33  \w   -124.00 -32.00   0.50    0.05    --  -52.00 -61.00-150.00  184
 34  \w     40.00 107.00   0.50    0.05    --  111.82-111.00  90.00  134
 35  \w    128.00 173.00   0.50    0.05    --  111.82  77.00-150.00   90
 36  \w     83.00 115.00   0.50    0.05    --  111.82  61.00-120.00   64
 37  \w     77.00 103.00   0.50    0.05    --  111.82  77.00-150.00   52
 38  \w     47.00  96.00   0.50    0.05    --  111.82-111.00  60.00   98
 39  \w    143.00 174.00   0.50    0.05    --  111.82  45.00-120.00   62
 40  \w     78.00 170.00   0.50    0.05    --  111.82  77.00-180.00  184
 41  \w     41.00  51.50   0.50    0.05    --  111.82 -61.00 -30.00   21
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1679963000
_diffrn_orient_matrix_UB_12      0.0330629000
_diffrn_orient_matrix_UB_13      0.0174460000
_diffrn_orient_matrix_UB_21      -0.0068376000
_diffrn_orient_matrix_UB_22      0.0762426000
_diffrn_orient_matrix_UB_23      -0.0581686000
_diffrn_orient_matrix_UB_31      -0.0629623000
_diffrn_orient_matrix_UB_32      -0.0963392000
_diffrn_orient_matrix_UB_33      -0.0401151000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0205
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            19124
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.765
_diffrn_reflns_theta_min         4.181
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.692
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76252
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1893 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4520
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0259
_refine_ls_R_factor_gt           0.0257
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0400P)^2^+0.6050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0683
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                4491
_reflns_number_total             4520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00722g2.cif
_cod_data_source_block           3ba
_cod_depositor_comments          'Adding full bibliography for 7159391.cif.'
_cod_database_code               7159391
_diffrn_oxdiff_digest_frames
;
01169126a0c9a1060810295ff560226a5901382c1ab
;
_diffrn_oxdiff_digest_hkl
;
012fc89a59517553e1bd4632b68bc49f41f39b
;
_reflns_odcompleteness_completeness 99.96
_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 N(H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N1(H1), C2(H2A), C22(H22), C11(H11), C6(H6), C18(H18), C14(H14),
 C19(H19), C3(H3), C12(H12), C21(H21), C5(H5), C4(H4), C13(H13), C20(H20)
;
_shelx_shelxl_version_number     2016/6
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.453
_oxdiff_exptl_absorpt_empirical_full_min 0.743