Regio- and Stereocontrolled Synthesis of 3-Substituted 1,2-Diazetidines by Asymmetric Allylic Amination of Vinyl Epoxide.
Rajkumar, Sundaram; Clarkson, Guy J.; Shipman, Michael; Organic letters 19 (2017) 2058–2061; doi:10.1021/acs.orglett.7b00653

data_1545935
_publ_section_title
;
 Regio- and Stereocontrolled Synthesis of 3-Substituted 1,2-Diazetidines
 by Asymmetric Allylic Amination of Vinyl Epoxide.
;
_journal_issue                   8
_journal_name_full               'Organic letters'
_journal_page_first              2058
_journal_page_last               2061
_journal_paper_doi               10.1021/acs.orglett.7b00653
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H22 N2 O6 S'
_chemical_formula_sum            'C21 H22 N2 O6 S'
_chemical_formula_weight         430.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 123.5490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.0091(5)
_cell_length_b                   6.21570(10)
_cell_length_c                   15.4618(2)
_cell_measurement_reflns_used    7091
_cell_measurement_temperature    175(2)
_cell_measurement_theta_max      76.8230
_cell_measurement_theta_min      5.7130
_cell_volume                     2083.22(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      175(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2833
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -87.00 -61.00   1.00   25.00    --  -41.71 128.00   0.00   26
  2  \w    -69.00  31.00   1.00   25.00    --  -41.71  57.00-120.00  100
  3  \w    -65.00  29.00   1.00   25.00    --  -41.71  57.00 150.00   94
  4  \w     10.00  46.00   1.00   25.00    --   41.71  77.00 -90.00   36
  5  \w     49.00  77.00   1.00   25.00    --   41.71  38.00 -60.00   28
  6  \w     12.00  70.00   1.00   25.00    --   41.71  77.00 -30.00   58
  7  \w      8.00  36.00   1.00   25.00    --   41.71  19.00 -60.00   28
  8  \w     25.00  68.00   1.00   25.00    --   41.71  57.00  60.00   43
  9  \w     15.00  58.00   1.00   25.00    --   41.71  57.00  30.00   43
 10  \w     19.00  70.00   1.00   25.00    --   41.71  38.00-120.00   51
 11  \w     14.00  89.00   1.00   25.00    --   41.71  57.00 -60.00   75
 12  \w     85.00 111.00   1.00  100.00    --  114.00  61.00   0.00   26
 13  \w     85.00 111.00   1.00  100.00    --  114.00  61.00 -60.00   26
 14  \w     81.00 107.00   1.00  100.00    --  114.00  77.00 -30.00   26
 15  \w    119.00 145.00   1.00  100.00    --  114.00  61.00 -90.00   26
 16  \w     32.00 107.00   1.00  100.00    --  114.00 -95.00-150.00   75
 17  \w     85.00 110.00   1.00  100.00    --  114.00  61.00 -90.00   25
 18  \w    119.00 146.00   1.00  100.00    --  114.00 -77.00 -60.00   27
 19  \w     81.00 107.00   1.00  100.00    --  114.00  77.00-120.00   26
 20  \w    130.00 158.00   1.00  100.00    --  114.00  77.00 -60.00   28
 21  \w     92.00 117.00   1.00  100.00    --  114.00  45.00-150.00   25
 22  \w    128.00 175.00   1.00  100.00    --  114.00  77.00-120.00   47
 23  \w     81.00 107.00   1.00  100.00    --  114.00  77.00 150.00   26
 24  \w     85.00 112.00   1.00  100.00    --  114.00  61.00-150.00   27
 25  \w    126.00 153.00   1.00  100.00    --  114.00  61.00-150.00   27
 26  \w     85.00 111.00   1.00  100.00    --  114.00  61.00 -30.00   26
 27  \w    130.00 178.00   1.00  100.00    --  114.00  77.00 -90.00   48
 28  \w     81.00 107.00   1.00  100.00    --  114.00  77.00 -60.00   26
 29  \w    119.00 145.00   1.00  100.00    --  114.00  61.00-120.00   26
 30  \w     82.00 107.00   1.00  100.00    --  114.00  77.00 -90.00   25
 31  \w    128.00 178.00   1.00  100.00    --  114.00  77.00-150.00   50
 32  \w     59.00 107.00   1.00  100.00    --  114.00-111.00 120.00   48
 33  \w     92.00 162.00   1.00  100.00    --  114.00  45.00   0.00   70
 34  \w     88.00 114.00   1.00  100.00    --  114.00  45.00 -30.00   26
 35  \w     81.00 171.00   1.00  100.00    --  114.00  77.00   0.00   90
 36  \w     88.00 115.00   1.00  100.00    --  114.00  45.00 -60.00   27
 37  \w     86.00 111.00   1.00  100.00    --  114.00  61.00-180.00   25
 38  \w     81.00 107.00   1.00  100.00    --  114.00  77.00-150.00   26
 39  \w     88.00 115.00   1.00  100.00    --  114.00  45.00-120.00   27
 40  \w     87.00 112.00   1.00  100.00    --  114.00  30.00 -30.00   25
 41  \w     88.00 115.00   1.00  100.00    --  114.00  45.00 -90.00   27
 42  \w     89.00 114.00   1.00  100.00    --  114.00  45.00  30.00   25
 43  \w     89.00 116.00   1.00  100.00    --  114.00  30.00 -90.00   27
 44  \w     88.00 115.00   1.00  100.00    --  114.00  30.00 -60.00   27
 45  \w     88.00 157.00   1.00  100.00    --  114.00  30.00   0.00   69
 46  \w     85.00 112.00   1.00  100.00    --  114.00  61.00  30.00   27
 47  \w     39.00  67.00   1.00  100.00    --  114.00 -95.00-180.00   28
 48  \w    141.00 172.00   1.00  100.00    --  114.00  77.00 -30.00   31
 49  \w     81.00 108.00   1.00  100.00    --  114.00  77.00-180.00   27
 50  \w     86.00 111.00   1.00  100.00    --  114.00  61.00-120.00   25
 51  \w     39.00 101.00   1.00  100.00    --  114.00 -77.00 -60.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0572949000
_diffrn_orient_matrix_UB_12      -0.0031699000
_diffrn_orient_matrix_UB_13      0.0629635000
_diffrn_orient_matrix_UB_21      -0.0419069000
_diffrn_orient_matrix_UB_22      0.0168788000
_diffrn_orient_matrix_UB_23      0.0772575000
_diffrn_orient_matrix_UB_31      -0.0036013000
_diffrn_orient_matrix_UB_32      -0.2472345000
_diffrn_orient_matrix_UB_33      0.0044035000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11575
_diffrn_reflns_point_group_measured_fraction_full 0.829
_diffrn_reflns_point_group_measured_fraction_max 0.805
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.796
_diffrn_reflns_theta_min         4.079
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.736
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26368
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.188
_refine_diff_density_min         -0.151
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1263 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

Flack x: 0.031(10) (Shelxl 2014)
Hooft y: 0.032(8) (Olex2)
;
_refine_ls_abs_structure_Flack   0.031(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3572
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0289
_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^)+(0.0515P)^2^+0.3489P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.618
_reflns_Friedel_fraction_full    0.658
_reflns_Friedel_fraction_max     0.616
_reflns_number_gt                3488
_reflns_number_total             3572
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b00653_si_004.cif
_cod_data_source_block           rs1
_cod_database_code               1545935
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.59
_olex2_refinement_description
;
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
2.a Ternary CH refined with riding coordinates:
 C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C20(H20),
 C21(H21), C23(H23), C24(H24)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C25(H25A,H25B,H25C)
;
_shelx_shelxl_version_number     2014/7
_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 3.094
_oxdiff_exptl_absorpt_empirical_full_min 0.755