A Diverse Library of Chiral Cyclopropane Scaffolds via Chemoenzymatic Assembly and Diversification of Cyclopropyl Ketones.
Nam, Donggeon; Steck, Viktoria; Potenzino, Robert J.; Fasan, Rudi; Journal of the American Chemical Society  (2021) –; doi:10.1021/jacs.0c09504

data_4135552
_publ_section_title
;
 A Diverse Library of Chiral Cyclopropane Scaffolds via Chemoenzymatic
 Assembly and Diversification of Cyclopropyl Ketones.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c09504
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H17 Br O'
_chemical_formula_sum            'C18 H17 Br O'
_chemical_formula_weight         329.22
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-14
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.6740(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.38540(10)
_cell_length_b                   5.85390(10)
_cell_length_c                   17.0708(2)
_cell_measurement_reflns_used    18575
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.4790
_cell_measurement_theta_min      2.6180
_cell_volume                     736.512(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_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 0.994
_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     31.00 124.00   0.50    0.05    --   52.00  79.00  -4.78  186
  2  \w     29.00 121.00   0.50    0.05    --   49.87  77.00 -60.00  184
  3  \w     85.00 178.00   0.50    0.05    --  105.75  77.00-150.00  186
  4  \w     85.00 178.00   0.50    0.05    --  105.75  77.00-180.00  186
  5  \w     41.00 131.00   0.50    0.05    --   60.00  74.00-123.02  180
  6  \w     52.00 144.00   0.50    0.05    --   72.00  76.00 -47.28  184
  7  \w     85.00 178.00   0.50    0.05    --  105.75  77.00 -60.00  186
  8  \w     92.00 178.00   0.50    0.05    --  105.75  61.00 -60.00  172
  9  \w     92.00 178.00   0.50    0.05    --  105.75  61.00   0.00  172
 10  \w     92.00 178.00   0.50    0.05    --  105.75  61.00  30.00  172
 11  \w     45.00 136.00   0.50    0.05    --   64.00  73.00 166.34  182
 12  \w     47.00 139.00   0.50    0.05    --   68.00  77.00 123.30  184
 13  \w     31.00 124.00   0.50    0.05    --   52.00  77.00  70.86  186
 14  \w     98.00 175.00   0.50    0.05    --  105.75  15.00 150.00  154
 15  \w     98.00 178.00   0.50    0.05    --  105.75  30.00 120.00  160
 16  \w     98.00 175.00   0.50    0.05    --  105.75  15.00  60.00  154
 17  \w     92.00 178.00   0.50    0.05    --  105.75  61.00 -30.00  172
 18  \w     92.00 178.00   0.50    0.05    --  105.75  61.00-120.00  172
 19  \w     98.00 175.00   0.50    0.05    --  105.75  15.00-180.00  154
 20  \w     34.00 109.00   0.50    0.05    --  105.75 -94.00   0.00  150
 21  \w     49.00 116.00   0.50    0.05    --   49.87-159.00   7.00  134
 22  \w     49.00 139.00   0.50    0.05    --  105.75-159.00   7.00  180
 23  \w     34.00 116.00   0.50    0.05    --  105.75-125.00  30.00  164
 24  \w     34.00 116.00   0.50    0.05    --  105.75-125.00 -30.00  164
 25  \w     34.00 116.00   0.50    0.05    --  105.75-125.00-150.00  164
 26  \w     34.00 116.00   0.50    0.05    --  105.75-125.00-120.00  164
 27  \w     34.00 109.00   0.50    0.05    --  105.75 -94.00 -60.00  150
 28  \w     34.00 116.00   0.50    0.05    --  105.75-125.00 -60.00  164
 29  \w     34.00 116.00   0.50    0.05    --  105.75-125.00 120.00  164
 30  \w     34.00 113.00   0.50    0.05    --  105.75-118.00 160.00  158
 31  \w     27.00  92.00   0.50    0.05    --   49.87-118.00 160.00  130
 32  \w     34.00 109.00   0.50    0.05    --  105.75 -94.00 -30.00  150
 33  \w     34.00 109.00   0.50    0.05    --  105.75 -94.00-150.00  150
 34  \w     34.00  80.00   0.50    0.05    --  105.75 -61.00-180.00   92
 35  \w     34.00  80.00   0.50    0.05    --  105.75 -61.00-150.00   92
 36  \w     34.00  80.00   0.50    0.05    --  105.75 -61.00 -60.00   92
 37  \w     34.00  80.00   0.50    0.05    --  105.75 -61.00 -30.00   92
 38  \w     96.00 178.00   0.50    0.05    --  105.75 118.00-113.00  164
 39  \w     92.00 178.00   0.50    0.05    --  105.75 125.00 -90.00  172
 40  \w     69.00 164.00   0.50    0.05    --  105.75 159.00  39.00  190
 41  \w     92.00 178.00   0.50    0.05    --  105.75 125.00 150.00  172
 42  \w     69.00 121.00   0.50    0.05    --   49.87 159.00  39.00  104
 43  \w      7.00  34.00   0.50    0.05    --   36.00  95.00 147.58   54
 44  \w     13.00  40.00   0.50    0.05    --   40.00  91.00  83.04   54
 45  \w    -17.00  10.00   0.50    0.05    --   16.00 103.00 -36.48   54
 46  \w      9.00  40.00   0.50    0.05    --   36.00  91.00-127.98   62
 47  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00  30.00   58
 48  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00  90.00   58
 49  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00   0.00   58
 50  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00 -30.00   58
 51  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00 -60.00   58
 52  \w     -5.00  24.00   0.50    0.05    --  -49.87  19.00 -90.00   58
 53  \w    -44.00 -12.00   0.50    0.05    --  -84.25  45.00 -90.00   64
 54  \w    -87.00  -5.00   0.50    0.05    --  -49.87 118.00-113.00  164
 55  \w   -114.00 -27.00   0.50    0.05    --  -49.87 159.00  39.00  174
 56  \w    -87.00 -12.00   0.50    0.05    --  -84.25 118.00-113.00  150
 57  \w   -156.00 -75.00   0.50    0.05    --  -84.25-118.00 160.00  162
 58  \w   -121.00 -75.00   0.50    0.05    --  -49.87-118.00 160.00   92
 59  \w   -147.00 -47.00   0.50    0.05    --  -84.25-159.00   7.00  200
 60  \w   -121.00 -70.00   0.50    0.05    --  -49.87-125.00 -90.00  102
 61  \w   -121.00 -70.00   0.50    0.05    --  -49.87-125.00 -60.00  102
 62  \w   -121.00 -47.00   0.50    0.05    --  -49.87-159.00   7.00  148
 63  \w   -156.00 -63.00   0.50    0.05    --  -84.25 -77.00  90.00  186
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0058218000
_diffrn_orient_matrix_UB_12      -0.1115294000
_diffrn_orient_matrix_UB_13      -0.0818891000
_diffrn_orient_matrix_UB_21      -0.0849180000
_diffrn_orient_matrix_UB_22      0.2189495000
_diffrn_orient_matrix_UB_23      -0.0364085000
_diffrn_orient_matrix_UB_31      0.1909113000
_diffrn_orient_matrix_UB_32      0.0939772000
_diffrn_orient_matrix_UB_33      -0.0123336000
_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  0.0918
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24493
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.776
_diffrn_reflns_theta_min         2.594
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.729
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81146
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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    1.485
_exptl_crystal_description       plate
_exptl_crystal_F_000             336
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.594
_refine_diff_density_min         -0.637
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 1322 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.020(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         3103
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0513P)^2^+0.3785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0890
_refine_ls_wR_factor_ref         0.0892
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                3069
_reflns_number_total             3103
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            compound_8c.cif
_cod_data_source_block           fasdn04
_cod_database_code               4135552
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.447
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C1(H1), C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C14(H14), C15(H15), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              79831
_shelx_hkl_checksum              33380
_olex2_submission_original_sample_id fasdn04
_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 3.183
_oxdiff_exptl_absorpt_empirical_full_min 0.475