Highly stereoselective and enantiodivergent synthesis of cyclopropylphosphonates with engineered carbene transferases
Ren, Xinkun; Chandgude, Ajay L.; Carminati, Daniela M.; Shen, Zhuofan; Khare, Sagar D.; Fasan, Rudi; Chemical Science 13 (2022) 8550–8556; doi:10.1039/D2SC01965E

data_1567397
_publ_section_title
;
 Highly stereoselective and enantiodivergent synthesis of
 cyclopropylphosphonates with engineered carbene transferases
;
_journal_issue                   29
_journal_name_full               'Chemical Science'
_journal_page_first              8550
_journal_page_last               8556
_journal_paper_doi               10.1039/D2SC01965E
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H21 O4 P, 3(H2 O)'
_chemical_formula_sum            'C18 H27 O7 P'
_chemical_formula_weight         386.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-06-09
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-08-25 deposited with the CCDC.	2022-05-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.38640(10)
_cell_length_b                   7.84160(10)
_cell_length_c                   39.8125(7)
_cell_measurement_reflns_used    12722
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.1890
_cell_measurement_theta_min      2.3000
_cell_volume                     1993.79(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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 2018/2 (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   -122.00 -42.00   0.50    0.97    --  -49.87 -22.00 159.00  160
  2  \w   -156.00 -78.00   0.50    3.89    --  -84.25-112.00 -33.00  156
  3  \w    100.00 178.00   0.50    3.89    --  105.75 110.00 153.00  156
  4  \w     34.00 112.00   0.50    3.89    --  105.75-112.00 -33.00  156
  5  \w     97.00 178.00   0.50    3.89    --  105.75  22.00 -34.00  162
  6  \w    -30.00  22.00   0.50    0.97    --  -49.87  38.00 -30.00  104
  7  \w    -22.00   5.00   0.50    0.97    --   49.87 -19.00  30.00   54
  8  \w    -22.00   5.00   0.50    0.97    --   49.87 -19.00-150.00   54
  9  \w    -42.00 -12.00   0.50    3.89    --  -84.25  45.00-150.00   60
 10  \w     34.00 116.00   0.50    3.89    --  105.75-125.00-150.00  164
 11  \w     34.00 127.00   0.50    3.89    --  105.75 -77.00-180.00  186
 12  \w     34.00 116.00   0.50    3.89    --  105.75-125.00  90.00  164
 13  \w     34.00 127.00   0.50    3.89    --  105.75 -77.00 -30.00  186
 14  \w     34.00  87.00   0.50    3.89    --  105.75 -61.00 -60.00  106
 15  \w     98.00 164.00   0.50    3.89    --  105.75  15.00 -90.00  132
 16  \w     34.00  87.00   0.50    3.89    --  105.75 -61.00  30.00  106
 17  \w     34.00  87.00   0.50    3.89    --  105.75 -61.00-150.00  106
 18  \w     34.00  87.00   0.50    3.89    --  105.75 -61.00 -90.00  106
 19  \w     34.00  87.00   0.50    3.89    --  105.75 -61.00 -30.00  106
 20  \w   -121.00 -37.00   0.50    0.97    --  -49.87 -57.00  60.00  168
 21  \w   -121.00 -37.00   0.50    0.97    --  -49.87 -57.00 -30.00  168
 22  \w     29.00 121.00   0.50    0.97    --   49.87  77.00 150.00  184
 23  \w     98.00 164.00   0.50    3.89    --  105.75  15.00 150.00  132
 24  \w     98.00 164.00   0.50    3.89    --  105.75  15.00  90.00  132
;
_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      0.2303857000
_diffrn_orient_matrix_UB_12      0.0261159000
_diffrn_orient_matrix_UB_13      0.0102056000
_diffrn_orient_matrix_UB_21      0.0539256000
_diffrn_orient_matrix_UB_22      0.0508085000
_diffrn_orient_matrix_UB_23      -0.0363644000
_diffrn_orient_matrix_UB_31      -0.0466362000
_diffrn_orient_matrix_UB_32      0.1880261000
_diffrn_orient_matrix_UB_33      0.0084078000
_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  0.0536
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            24420
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.896
_diffrn_reflns_theta_min         2.219
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.534
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
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    1.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.386
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1537 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         4187
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0481P)^2^+1.3066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1090
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                3950
_reflns_number_total             4187
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01965e2.cif
_cod_data_source_block           fasxr01
_cod_database_code               1567397
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.799
_reflns_odcompleteness_completeness 99.96
_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, All O(H,H) groups
2.a Riding coordinates:
 O5(H5A,H5B), O6(H6A,H6B), O7(H7A,H7B)
2.b Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
2.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15)
2.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              57398
_olex2_submission_original_sample_id fasxr01
_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 1.522
_oxdiff_exptl_absorpt_empirical_full_min 0.625