Borohydride intermediates pave the way for magnesium-catalysed enantioselective ketone reduction.
Vasilenko, Vladislav; Blasius, Clemens K.; Wadepohl, Hubert; Gade, Lutz H.; Chemical communications (Cambridge, England) 56 (2020) 1203–1206; doi:10.1039/c9cc09111d

data_7125680
_publ_section_title
;
 Borohydride intermediates pave the way for magnesium-catalysed
 enantioselective ketone reduction.
;
_journal_issue                   8
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1203
_journal_page_last               1206
_journal_paper_doi               10.1039/c9cc09111d
_journal_volume                  56
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C38 H44 B Mg N3 O5'
_chemical_formula_sum            'C38 H44 B Mg N3 O5'
_chemical_formula_weight         657.88
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_vv33
_audit_creation_date             2018-09-10
_audit_creation_method
;
Olex2 1.2
(compiled May 29 2018 13:30:08 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-29 deposited with the CCDC.	2019-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.60635(16)
_cell_length_b                   16.6805(3)
_cell_length_c                   19.3703(2)
_cell_measurement_reflns_used    28087
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      29.9810
_cell_measurement_theta_min      2.4930
_cell_volume                     3426.98(9)
_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
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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     -4.00  97.00   0.50   15.00    --   26.43  77.00-120.00  202
  2  \w      5.00  95.00   0.50   15.00    --   26.43  57.00   0.00  180
  3  \w    -42.00  47.00   0.50   15.00    --   26.43 -57.00-150.00  178
  4  \w      5.00  95.00   0.50   15.00    --   26.43  57.00-180.00  180
  5  \w    -42.00  47.00   0.50   15.00    --   26.43 -57.00  30.00  178
  6  \w    -20.00  68.00   0.50   15.00    --   26.43 -99.00 -30.00  176
  7  \w     -4.00  97.00   0.50   15.00    --   26.43  77.00  60.00  202
  8  \w    -20.00  68.00   0.50   15.00    --   26.43 -99.00 150.00  176
  9  \w    -71.00 -36.00   0.50   15.00    --    2.00 150.00   1.66   70
 10  \w     -4.00  97.00   0.50   15.00    --   26.43  77.00 -30.00  202
 11  \w    -20.00  68.00   0.50   15.00    --   26.43 -99.00  30.00  176
 12  \w    -20.00  68.00   0.50   15.00    --   26.43 -99.00-180.00  176
 13  \w    -46.00  52.00   0.50   15.00    --   26.43 -38.00 -90.00  196
 14  \w    -46.00  52.00   0.50   15.00    --   26.43 -38.00  90.00  196
 15  \w     -4.00  97.00   0.50   15.00    --   26.43  77.00-150.00  202
 16  \w     -4.00  97.00   0.50   15.00    --   26.43  77.00-120.00  202
 17  \w     -4.00  97.00   0.50   15.00    --   26.43  77.00 -90.00  202
 18  \w     -4.00  85.50   0.50   15.00    --   26.43  77.00 -60.00  179
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0618536000
_diffrn_orient_matrix_UB_12      0.0147654000
_diffrn_orient_matrix_UB_13      -0.0057455000
_diffrn_orient_matrix_UB_21      0.0240569000
_diffrn_orient_matrix_UB_22      -0.0395804000
_diffrn_orient_matrix_UB_23      0.0023172000
_diffrn_orient_matrix_UB_31      -0.0083560000
_diffrn_orient_matrix_UB_32      -0.0048856000
_diffrn_orient_matrix_UB_33      -0.0360778000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            145176
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.522
_diffrn_reflns_theta_min         2.189
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.744
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1400
_exptl_crystal_size_max          0.232
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 3771 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         12099
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0496
_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^)+(0.0581P)^2^+0.8439P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                9996
_reflns_number_total             12099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc09111d2.cif
_cod_data_source_block           ga_vv33
_cod_depositor_comments
'Adding full bibliography for 7125679--7125681.cif.'
_cod_database_code               7125680
_audit_block_refno               3166
_audit_block_usercomment         'VV619 irregular yellow'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.990
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O5-C35A \\sim O5-C35B \\sim O5-C38
 with sigma of 0.02
 C35A-C36A \\sim C35B-C36B \\sim C38-C37A \\sim C38-C37B
 with sigma of 0.02
 C36A-C37A \\sim C36B-C37B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35A \\sim C36A \\sim C37A \\sim C35B \\sim C36B \\sim C37B
\\sim C38: within 1A with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O5, C35A, C36A, C37A, C35B, C36B, C37B, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C35B)=Sof(H35C)=Sof(H35D)=Sof(C36B)=Sof(H36C)=Sof(H36D)=Sof(C37B)=
 Sof(H37C)=Sof(H37D)=Sof(H38C)=Sof(H38D)=1-FVAR(1)
 Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(C37A)=
 Sof(H37A)=Sof(H37B)=Sof(H38A)=Sof(H38B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C11(H11A,H11B), C35A(H35A,H35B), C36A(H36A,H36B), C37A(H37A,
 H37B), C35B(H35C,H35D), C36B(H36C,H36D), C37B(H37C,H37D), C38(H38A,H38B),
 C38(H38C,H38D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
6.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.112
_oxdiff_exptl_absorpt_empirical_full_min 0.885
_shelx_res_checksum              75399
_cell_oxdiff_length_a            10.6038(3)
_cell_oxdiff_length_b            16.6790(3)
_cell_oxdiff_length_c            19.3767(5)
_cell_oxdiff_angle_alpha         89.9895(18)
_cell_oxdiff_angle_beta          90.043(2)
_cell_oxdiff_angle_gamma         90.0390(18)
_cell_oxdiff_volume              3426.98(14)
_cell_oxdiff_measurement_reflns_used 28087