Desymmetrization of Cyclopropenes via the Potassium-Templated Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial Activity.
Maslivetc, Vladimir A.; Turner, Danielle N.; McNair, Kimberly N.; Frolova, Liliya; Rogelj, Snezna; Maslivetc, Anna A.; Aksenov, Nicolai A.; Rubina, Marina; Rubin, Michael; The Journal of organic chemistry 83 (2018) 5650–5664; doi:10.1021/acs.joc.8b00640

data_4034782
_publ_section_title
;
 Desymmetrization of Cyclopropenes via the Potassium-Templated
 Diastereoselective 7- exo- trig Cycloaddition of Tethered Amino Alcohols
 toward Enantiopure Cyclopropane-Fused Oxazepanones with Antimycobacterial
 Activity.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5650
_journal_page_last               5664
_journal_paper_doi               10.1021/acs.joc.8b00640
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H19 Cl2 N O2'
_chemical_formula_sum            'C20 H19 Cl2 N O2'
_chemical_formula_weight         376.26
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.52861(9)
_cell_length_b                   7.52861(9)
_cell_length_c                   32.1688(9)
_cell_measurement_reflns_used    25875
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.5940
_cell_measurement_theta_min      5.4340
_cell_volume                     1823.33(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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.9988
_diffrn_measured_fraction_theta_max 0.9120
_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   -114.00 -14.00   1.00    1.59    --  -41.85 -57.00 -90.00  100
  2  \w   -116.00 -17.00   1.00    1.59    --  -41.85 -38.00   0.00   99
  3  \w   -115.00 -57.00   1.00    1.59    --  -41.85-150.00  10.00   58
  4  \w    -96.00  -2.00   1.00    1.59    --  -41.85 125.00 150.00   94
  5  \w    -95.00   0.00   1.00    1.59    --  -41.85 123.00-106.00   95
  6  \w   -116.00 -17.00   1.00    1.59    --  -41.85 -38.00 150.00   99
  7  \w     34.00 121.00   1.00    6.34    --  106.96-125.00 -90.00   87
  8  \w     31.00 140.00   1.00    6.34    --  106.96 -77.00-150.00  109
  9  \w     33.00 121.00   1.00    6.34    --  106.96-123.00 173.00   88
 10  \w     31.00 135.00   1.00    6.34    --  106.96 -30.00-150.00  104
 11  \w     31.00 140.00   1.00    6.34    --  106.96 -77.00  60.00  109
 12  \w     31.00 135.00   1.00    6.34    --  106.96 -30.00  30.00  104
 13  \w     34.00 133.00   1.00    6.34    --  106.96 -45.00 -60.00   99
 14  \w     25.00 160.00   1.00    6.34    --  106.96 -15.00 120.00  135
 15  \w     25.00 109.00   1.00    6.34    --  106.96 -95.00   0.00   84
 16  \w     81.00 178.00   1.00    6.34    --  106.96  45.00-180.00   97
 17  \w   -118.00  -9.00   1.00    1.59    --  -41.85 -77.00 120.00  109
 18  \w   -118.00  -9.00   1.00    1.59    --  -41.85 -77.00-120.00  109
 19  \w   -118.00  -9.00   1.00    1.59    --  -41.85 -77.00-180.00  109
 20  \w   -118.00  -9.00   1.00    1.59    --  -41.85 -77.00   0.00  109
 21  \w      1.00  83.00   1.00    1.59    --   41.85 -99.00  30.00   82
 22  \w     54.00 178.00   1.00    6.34    --  106.96  15.00  30.00  124
 23  \w     74.00 178.00   1.00    6.34    --  106.96  77.00   0.00  104
 24  \w     79.00 178.00   1.00    6.34    --  106.96  30.00 -90.00   99
 25  \w     74.00 178.00   1.00    6.34    --  106.96  77.00 -90.00  104
 26  \w     78.00 178.00   1.00    6.34    --  106.96  61.00-150.00  100
 27  \w     74.00 178.00   1.00    6.34    --  106.96  77.00  60.00  104
 28  \w     74.00 178.00   1.00    6.34    --  106.96  77.00 120.00  104
 29  \w     74.00 178.00   1.00    6.34    --  106.96  77.00  30.00  104
 30  \w     81.00 178.00   1.00    6.34    --  106.96  45.00 120.00   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1112964000
_diffrn_orient_matrix_UB_12      0.1698719000
_diffrn_orient_matrix_UB_13      -0.0058344000
_diffrn_orient_matrix_UB_21      -0.1709745000
_diffrn_orient_matrix_UB_22      0.1121522000
_diffrn_orient_matrix_UB_23      0.0002680000
_diffrn_orient_matrix_UB_31      0.0146900000
_diffrn_orient_matrix_UB_32      0.0201315000
_diffrn_orient_matrix_UB_33      0.0475628000
_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  0.0329
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            33608
_diffrn_reflns_point_group_measured_fraction_full 0.924
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.962
_diffrn_reflns_theta_min         5.501
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.306
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60706
_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_density_diffrn    1.371
_exptl_crystal_F_000             784
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1490 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3396
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0289
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0468P)^2^+0.3027P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0756
_refine_ls_wR_factor_ref         0.0758
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    0.845
_reflns_Friedel_fraction_max     0.831
_reflns_number_gt                3378
_reflns_number_total             3396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00640_si_003.cif
_cod_data_source_block           anna16122016_vm215_8
_cod_original_cell_volume        1823.33(7)
_cod_database_code               4034782
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C011(H011), C014(H014), C018(H018)
2.b Secondary CH2 refined with riding coordinates:
 C024(H02D,H02E)
2.c Aromatic/amide H refined with riding coordinates:
 C005(H005), C008(H008), C012(H012), C013(H013), C020(H020), C021(H021),
 C022(H022), C025(H025)
2.d Idealised Me refined as rotating group:
 C017(H01A,H01B,H01C), C023(H02A,H02B,H02C)
;
_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 2.159
_oxdiff_exptl_absorpt_empirical_full_min 0.471