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_4128744
_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 Cl O2'
_chemical_formula_sum            'C11 H9 Cl O2'
_chemical_formula_weight         208.63
_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             2018-12-10
_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                 96.864(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.51150(10)
_cell_length_b                   9.7152(2)
_cell_length_c                   8.7681(2)
_cell_measurement_reflns_used    8075
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      76.6360
_cell_measurement_theta_min      5.0800
_cell_volume                     466.126(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      99.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_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    -54.00 -29.00   0.50    0.05    --  -49.87 -77.00  30.00   50
  2  \w    -73.00 -31.00   0.50    0.05    --  -49.87 -77.00 120.00   84
  3  \w    -87.00 -61.00   0.50    0.05    --  -84.25 -82.00 118.79   52
  4  \w    -89.00 -63.00   0.50    0.05    --  -84.25 -77.00 150.00   52
  5  \w    -99.00 -64.00   0.50    0.05    --  -84.25 -77.00  90.00   70
  6  \w    -95.00 -68.00   0.50    0.05    --  -84.25 -77.00  30.00   54
  7  \w    -92.00 -63.00   0.50    0.05    --  -84.25 -77.00   0.00   58
  8  \w    -90.00 -64.00   0.50    0.05    --  -84.25 -77.00 -60.00   52
  9  \w    -90.00 -65.00   0.50    0.05    --  -84.25 -77.00 -90.00   50
 10  \w    -88.00 -62.00   0.50    0.05    --  -84.25 -83.00-141.73   52
 11  \w    -89.00 -63.00   0.50    0.05    --  -84.25 -77.00-180.00   52
 12  \w    -91.00 -65.00   0.50    0.05    --  -84.25 -73.00-129.57   52
 13  \w    -94.00 -63.00   0.50    0.05    --  -84.25 -79.00 -67.06   62
 14  \w    -88.00 -63.00   0.50    0.05    --  -84.25 -77.00 -30.00   50
 15  \w   -105.00 -69.00   0.50    0.05    --  -49.87 -77.00  30.00   72
 16  \w   -110.00 -85.00   0.50    0.05    --  -84.25-135.00  51.00   50
 17  \w   -117.00 -92.00   0.50    0.05    --  -49.87-135.00  51.00   50
 18  \w    -95.00 -64.00   0.50    0.05    --  -84.25 -77.00  60.00   62
 19  \w    -94.00 -67.00   0.50    0.05    --  -84.25 -77.00  47.46   54
 20  \w    -94.00 -69.00   0.50    0.05    --  -84.25 -77.00  80.56   50
 21  \w   -104.00 -66.00   0.50    0.05    --  -84.25 -72.00 129.47   76
 22  \w   -145.00-120.00   0.50    0.05    --  -84.25 -77.00 -30.00   50
 23  \w    -79.00 -39.00   0.50    0.05    --  -49.87 -57.00 -90.00   80
 24  \w    -54.00 -29.00   0.50    0.05    --  -49.87 -77.00-120.00   50
 25  \w    -54.00 -29.00   0.50    0.05    --  -49.87 -77.00-180.00   50
 26  \w   -106.00 -79.00   0.50    0.05    --  -49.87 -77.00-180.00   54
 27  \w   -117.00 -92.00   0.50    0.05    --  -49.87-134.00-129.00   50
 28  \w   -118.00 -92.00   0.50    0.05    --  -49.87 -77.00-120.00   52
 29  \w   -108.00 -71.00   0.50    0.05    --  -84.25 -57.00-136.97   74
 30  \w   -151.00-100.00   0.50    0.05    --  -84.25-134.00-129.00  102
 31  \w     44.00  98.00   0.50    0.05    --   49.87-134.00-129.00  108
 32  \w     72.00 107.00   0.50    0.05    --  105.75-134.00-129.00   70
 33  \w     72.00  98.00   0.50    0.05    --  105.75 -94.00-120.00   52
 34  \w     72.00 125.00   0.50    0.05    --  105.75 -77.00-120.00  106
 35  \w     88.00 127.00   0.50    0.05    --  105.75 -77.00 -30.00   78
 36  \w     68.00  93.00   0.50    0.05    --   49.87-135.00  51.00   50
 37  \w     41.00 119.00   0.50    0.05    --  105.75-135.00  51.00  156
 38  \w     55.00 127.00   0.50    0.05    --  105.75 -77.00  60.00  144
 39  \w    135.00 175.00   0.50    0.05    --  105.75  15.00 -60.00   80
 40  \w    136.00 162.00   0.50    0.05    --  105.75  77.00 -60.00   52
 41  \w    153.00 178.00   0.50    0.05    --  105.75  77.00 -90.00   50
 42  \w    148.00 175.00   0.50    0.05    --  105.75  77.00-120.00   54
 43  \w    143.00 178.00   0.50    0.05    --  105.75  77.00-150.00   70
 44  \w    140.00 168.00   0.50    0.05    --  105.75  61.00-180.00   56
 45  \w    106.00 134.00   0.50    0.05    --  105.75 134.00 -62.00   56
 46  \w     90.00 118.00   0.50    0.05    --  105.75  77.00-120.00   56
 47  \w     89.00 118.00   0.50    0.05    --  105.75  77.00 -60.00   58
 48  \w    135.00 177.00   0.50    0.05    --  105.75  77.00 -30.00   84
 49  \w    133.00 158.00   0.50    0.05    --  105.75  77.00  30.00   50
 50  \w    147.00 177.00   0.50    0.05    --  105.75  45.00  90.00   60
 51  \w    151.00 177.00   0.50    0.05    --  105.75  77.00 120.00   52
 52  \w    133.00 177.00   0.50    0.05    --  105.75  77.00 150.00   88
 53  \w    130.00 155.00   0.50    0.05    --  105.75 135.00 117.00   50
 54  \w    125.00 150.00   0.50    0.05    --  105.75  77.00 120.00   50
 55  \w    101.00 161.00   0.50    0.05    --  105.75  45.00  60.00  120
 56  \w     96.00 122.00   0.50    0.05    --  105.75  61.00   0.00   52
 57  \w     85.00 120.00   0.50    0.05    --  105.75  77.00  30.00   70
 58  \w     90.00 117.00   0.50    0.05    --  105.75  77.00 -30.00   54
 59  \w     90.00 131.00   0.50    0.05    --  105.75  77.00 -90.00   82
 60  \w     93.00 141.00   0.50    0.05    --  105.75  61.00-150.00   96
 61  \w     94.00 119.00   0.50    0.05    --   49.87  77.00-180.00   50
 62  \w     86.00 139.00   0.50    0.05    --  105.75  77.00-150.00  106
 63  \w     94.00 125.00   0.50    0.05    --  105.75  61.00-180.00   62
 64  \w     98.00 130.00   0.50    0.05    --  105.75  15.00 -60.00   64
 65  \w     89.00 175.00   0.50    0.05    --  105.75  77.00   0.00  172
 66  \w     98.00 140.00   0.50    0.05    --  105.75  45.00  90.00   84
 67  \w     88.00 116.00   0.50    0.05    --  105.75  77.00 150.00   56
 68  \w     85.00 116.00   0.50    0.05    --  105.75  77.00 120.00   62
 69  \w     85.00 146.00   0.50    0.05    --  105.75  77.00  90.00  122
 70  \w     92.00 142.00   0.50    0.05    --  105.75  61.00 120.00  100
 71  \w     57.00  84.00   0.50    0.05    --   49.87  38.00 -30.00   54
 72  \w     42.00  75.00   0.50    0.05    --   49.87  38.00 -60.00   66
 73  \w     29.00  59.00   0.50    0.05    --   49.87  77.00-120.00   60
 74  \w     42.00  75.00   0.50    0.05    --   49.87  38.00-150.00   66
 75  \w     29.00  55.00   0.50    0.05    --   49.87  77.00-180.00   52
 76  \w     29.00  54.00   0.50    0.05    --   49.87  77.00 -30.00   50
 77  \w     42.00  87.00   0.50    0.05    --   49.87  38.00  30.00   90
 78  \w     44.00  74.00   0.50    0.05    --   49.87  38.00  90.00   60
 79  \w     33.00  59.00   0.50    0.05    --   49.87  77.00   0.00   52
 80  \w     30.00  55.00   0.50    0.05    --   49.87  77.00  30.00   50
 81  \w     31.00  58.00   0.50    0.05    --   49.87  77.00  60.00   54
 82  \w     29.00  60.00   0.50    0.05    --   49.87  77.00 120.00   62
 83  \w     40.00  70.00   0.50    0.05    --  105.75 -30.00  90.00   60
 84  \w     43.00  71.00   0.50    0.05    --  105.75 -30.00  60.00   56
 85  \w     47.00  88.00   0.50    0.05    --  105.75 -45.00   0.00   82
 86  \w     34.00  90.00   0.50    0.05    --  105.75 -45.00-120.00  112
 87  \w     36.00  98.00   0.50    0.05    --  105.75 -77.00-180.00  124
 88  \w     36.00  67.00   0.50    0.05    --  105.75 -77.00-120.00   62
 89  \w    -64.00 -37.00   0.50    0.05    --  -49.87 134.00 -62.00   54
 90  \w    -64.00 -39.00   0.50    0.05    --  -49.87 135.00 117.00   50
 91  \w    -81.00 -56.00   0.50    0.05    --  -84.25 135.00 117.00   50
;
_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      -0.0469544000
_diffrn_orient_matrix_UB_12      0.0121006000
_diffrn_orient_matrix_UB_13      -0.1762687000
_diffrn_orient_matrix_UB_21      0.0040200000
_diffrn_orient_matrix_UB_22      0.1581369000
_diffrn_orient_matrix_UB_23      0.0135478000
_diffrn_orient_matrix_UB_31      0.2774763000
_diffrn_orient_matrix_UB_32      -0.0002775000
_diffrn_orient_matrix_UB_33      -0.0085445000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.0328
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_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            11264
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.720
_diffrn_reflns_theta_min         5.081
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.365
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43353
_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    1.486
_exptl_crystal_description       needle
_exptl_crystal_F_000             216
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.247
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 874 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     127
_refine_ls_number_reflns         1947
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0478P)^2^+0.0768P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0804
_refine_ls_wR_factor_ref         0.0806
_reflns_Friedel_coverage         0.863
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                1930
_reflns_number_total             1947
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02700_si_003.cif
_cod_data_source_block           fasac10
_cod_database_code               4128744
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.287
_reflns_odcompleteness_completeness 99.90
_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              26798
_shelx_hkl_checksum              91302
_olex2_submission_original_sample_id fasac10
_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 2.977
_oxdiff_exptl_absorpt_empirical_full_min 0.530