Stereodivergent Intramolecular Cyclopropanation Enabled by Engineered Carbene Transferases.
Chandgude, Ajay L.; Ren, Xinkun; Fasan, Rudi; Journal of the American Chemical Society 141 (2019) 9145–9150; doi:10.1021/jacs.9b02700

data_4128745
_publ_section_title
;
 Stereodivergent Intramolecular Cyclopropanation Enabled by Engineered
 Carbene Transferases.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9145
_journal_page_last               9150
_journal_paper_doi               10.1021/jacs.9b02700
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C11 H9 Br O2'
_chemical_formula_sum            'C11 H9 Br O2'
_chemical_formula_weight         253.09
_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             2018-12-09
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.545(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.61190(10)
_cell_length_b                   9.6719(2)
_cell_length_c                   8.9813(2)
_cell_measurement_reflns_used    9494
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.0800
_cell_measurement_theta_min      4.9790
_cell_volume                     483.264(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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     42.00 121.00   0.50    0.05    --   49.12  38.00 -30.00  158
  2  \w     98.00 178.00   0.50    0.06    --  105.75  89.00 -31.00  160
  3  \w    134.00 160.00   0.50    0.06    --  105.75  61.00 -90.00   52
  4  \w    114.00 140.00   0.50    0.06    --  105.75  77.00   0.00   52
  5  \w    137.00 166.00   0.50    0.06    --  105.75  77.00  30.00   58
  6  \w    127.00 152.00   0.50    0.06    --  105.75  61.00  30.00   50
  7  \w     95.00 135.00   0.50    0.06    --  105.75  61.00  90.00   80
  8  \w    130.00 177.00   0.50    0.06    --  105.75  61.00 120.00   94
  9  \w    141.00 177.00   0.50    0.06    --  105.75  61.00 150.00   72
 10  \w     98.00 171.00   0.50    0.06    --  105.75  61.00  60.00  146
 11  \w     88.00 128.00   0.50    0.06    --  105.75  77.00 150.00   80
 12  \w     85.00 119.00   0.50    0.06    --  105.75  77.00 120.00   68
 13  \w     93.00 134.00   0.50    0.06    --  105.75  61.00 150.00   82
 14  \w     92.00 123.00   0.50    0.06    --  105.75  61.00 120.00   62
 15  \w     86.00 115.00   0.50    0.06    --  105.75  77.00  60.00   58
 16  \w     97.00 124.00   0.50    0.06    --  105.75  61.00  30.00   54
 17  \w     93.00 142.00   0.50    0.06    --  105.75  61.00   0.00   98
 18  \w     86.00 177.00   0.50    0.06    --  105.75  77.00 -60.00  182
 19  \w     96.00 121.00   0.50    0.06    --  105.75  61.00 -90.00   50
 20  \w     93.00 152.00   0.50    0.06    --  105.75  61.00 -60.00  118
 21  \w     97.00 164.00   0.50    0.06    --  105.75  61.00-150.00  134
 22  \w     94.00 122.00   0.50    0.06    --  105.75  61.00-180.00   56
 23  \w     85.00 171.00   0.50    0.06    --  105.75  77.00-120.00  172
 24  \w     89.00 128.00   0.50    0.06    --  105.75  77.00 -90.00   78
 25  \w     89.00 147.00   0.50    0.06    --  105.75  77.00-150.00  116
 26  \w     86.00 125.00   0.50    0.06    --  105.75  77.00-180.00   78
 27  \w     42.00 121.00   0.50    0.05    --   49.12  38.00 -60.00  158
 28  \w     85.00 112.00   0.50    0.06    --  105.75  77.00   0.00   54
 29  \w     87.00 122.00   0.50    0.06    --  105.75  77.00  30.00   70
 30  \w     29.00 120.00   0.50    0.05    --   49.12  77.00  30.00  182
 31  \w     37.00 120.00   0.50    0.05    --   49.12  57.00  90.00  166
 32  \w     37.00 120.00   0.50    0.05    --   49.12  57.00   0.00  166
 33  \w     37.00 120.00   0.50    0.05    --   49.12  57.00 120.00  166
 34  \w     37.00 120.00   0.50    0.05    --   49.12  57.00  30.00  166
 35  \w     37.00  82.00   0.50    0.06    --  105.75 -15.00-120.00   90
 36  \w     83.00 125.00   0.50    0.06    --  105.75 -77.00-120.00   84
 37  \w     80.00 116.00   0.50    0.06    --  105.75-125.00-120.00   72
 38  \w     58.00 116.00   0.50    0.06    --  105.75-125.00-180.00  116
 39  \w     34.00 132.00   0.50    0.06    --  105.75 -89.00-146.00  196
 40  \w     58.00 119.00   0.50    0.06    --  105.75 -61.00   0.00  122
 41  \w     79.00 105.00   0.50    0.06    --  105.75-125.00  30.00   52
 42  \w     87.00 116.00   0.50    0.06    --  105.75-125.00  90.00   58
 43  \w     59.00  88.00   0.50    0.06    --  105.75 -94.00 120.00   58
 44  \w     57.00  88.00   0.50    0.06    --  105.75 -45.00 120.00   62
 45  \w     35.00  71.00   0.50    0.06    --  105.75 -30.00  30.00   72
 46  \w     35.00  89.00   0.50    0.06    --  105.75 -45.00  90.00  108
 47  \w     37.00 112.00   0.50    0.06    --  105.75-125.00  60.00  150
 48  \w     36.00  68.00   0.50    0.06    --  105.75 -45.00 -60.00   64
 49  \w     36.00  71.00   0.50    0.06    --  105.75 -77.00-120.00   70
 50  \w     35.00  84.00   0.50    0.06    --  105.75 -45.00-180.00   98
 51  \w     31.00  95.00   0.50    0.05    --   49.12-125.00-150.00  128
 52  \w     36.00  85.00   0.50    0.06    --  105.75 -45.00-120.00   98
 53  \w     42.00 122.00   0.50    0.05    --   49.12  19.00-150.00  160
 54  \w     29.00 120.00   0.50    0.05    --   49.12  77.00-120.00  182
 55  \w     37.00 120.00   0.50    0.05    --   49.12  57.00-150.00  166
 56  \w     29.00 120.00   0.50    0.05    --   49.12  77.00 -90.00  182
 57  \w     29.00 120.00   0.50    0.05    --   49.12  77.00  90.00  182
 58  \w     29.00 120.00   0.50    0.05    --   49.12  77.00 120.00  182
 59  \w     29.00 120.00   0.50    0.05    --   49.12  77.00 -30.00  182
 60  \w    -22.00  75.00   0.50    0.05    --   49.12 -89.00-146.00  194
 61  \w     38.00  82.00   0.50    0.06    --  105.75-125.00  90.00   88
 62  \w    -75.00  23.00   0.50    0.05    --  -49.12  89.00 -31.00  196
 63  \w    -98.00 -63.00   0.50    0.06    --  -84.25 -77.00  -1.58   70
 64  \w    -93.00 -63.00   0.50    0.06    --  -84.25 -81.00 -45.36   60
 65  \w    -91.00 -65.00   0.50    0.06    --  -84.25 -79.00 -29.60   52
 66  \w   -101.00 -68.00   0.50    0.06    --  -84.25 -65.00 -29.16   66
 67  \w   -120.00 -28.00   0.50    0.05    --  -49.12 -77.00-120.00  184
 68  \w    -91.00 -65.00   0.50    0.06    --  -84.25 -77.00-180.00   52
 69  \w    -99.00 -66.00   0.50    0.06    --  -84.25 -73.00-141.91   66
 70  \w   -120.00 -36.00   0.50    0.05    --  -49.12 -57.00-120.00  168
 71  \w   -110.00 -12.00   0.50    0.06    --  -84.25  89.00 -31.00  196
 72  \w   -103.00 -73.00   0.50    0.06    --  -84.25 -59.00 174.60   60
 73  \w   -121.00 -42.00   0.50    0.05    --  -49.12 -19.00 150.00  158
 74  \w   -120.00 -28.00   0.50    0.05    --  -49.12 -77.00 120.00  184
 75  \w   -156.00 -76.00   0.50    0.06    --  -84.25 -89.00-146.00  160
 76  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00-120.00  186
 77  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00-150.00  186
 78  \w   -156.00 -61.00   0.50    0.06    --  -84.25 -83.00 -99.80  190
 79  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00  30.00  186
 80  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00 150.00  186
 81  \w   -156.00 -68.00   0.50    0.06    --  -84.25 -65.00 114.21  176
 82  \w   -156.00 -61.00   0.50    0.06    --  -84.25 -83.00  56.45  190
 83  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00  90.00  186
 84  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -77.00 -60.00  186
 85  \w   -156.00 -63.00   0.50    0.06    --  -84.25 -79.00 -80.22  186
 86  \w   -156.00 -64.00   0.50    0.06    --  -84.25 -75.00  96.55  184
 87  \w   -156.00 -65.00   0.50    0.06    --  -84.25 -74.00  48.98  182
;
_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      -0.0481129000
_diffrn_orient_matrix_UB_12      -0.0041427000
_diffrn_orient_matrix_UB_13      -0.1728551000
_diffrn_orient_matrix_UB_21      -0.1145651000
_diffrn_orient_matrix_UB_22      0.1448170000
_diffrn_orient_matrix_UB_23      -0.0009528000
_diffrn_orient_matrix_UB_31      0.2474581000
_diffrn_orient_matrix_UB_32      0.0661148000
_diffrn_orient_matrix_UB_33      -0.0086234000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0941
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            19153
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.000
_diffrn_reflns_theta_min         4.967
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.547
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.739
_exptl_crystal_description       plate
_exptl_crystal_F_000             252
_exptl_crystal_size_max          0.334
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.026
_refine_diff_density_max         1.194
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Flack x determined using 889 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     127
_refine_ls_number_reflns         2023
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0693P)^2^+0.4286P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1097
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.865
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                1978
_reflns_number_total             2023
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02700_si_004.cif
_cod_data_source_block           fasac09
_cod_database_code               4128745
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.259
_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
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11)
;
_shelx_res_checksum              13658
_shelx_hkl_checksum              36627
_olex2_submission_original_sample_id fasac09
_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 1.753
_oxdiff_exptl_absorpt_empirical_full_min 0.541