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_7125681
_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         'C44 H46 F Mg N3 O5'
_chemical_formula_sum            'C44 H46 F Mg N3 O5'
_chemical_formula_weight         740.15
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_vv35
_audit_creation_date             2018-11-09
_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                65.663(3)
_cell_angle_beta                 88.065(3)
_cell_angle_gamma                84.019(3)
_cell_formula_units_Z            1
_cell_length_a                   9.5675(4)
_cell_length_b                   9.7347(4)
_cell_length_c                   11.4970(3)
_cell_measurement_reflns_used    16003
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.5300
_cell_measurement_theta_min      4.2080
_cell_volume                     970.28(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.20a (Rigaku OD, 2018)'
_computing_publication_material
'encif (Wadepohl, 2009-18); encifer 1.6.x (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_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    -69.00  21.00   1.00    5.00    --    0.00 -57.00 -30.00   90
  2  \w    -21.00  69.00   1.00    5.00    --    0.00  57.00-120.00   90
  3  \w    -21.00  69.00   1.00    5.00    --    0.00  57.00 120.00   90
  4  \w    -35.00  14.00   1.00    5.00    --   10.00 106.00 133.46   49
  5  \w    -39.00   4.00   1.00    5.00    --   14.00 118.00 -86.04   43
  6  \w    -37.00   1.00   1.00    5.00    --   18.00 122.00  14.40   38
  7  \w    -10.00  17.00   1.00   10.00    --   34.00 103.00  65.76   27
  8  \w     -1.00  27.00   1.00   10.00    --   38.00  93.00-106.78   28
  9  \w      6.00  33.00   1.00   10.00    --   42.00  88.00  88.61   27
 10  \w      6.00  33.00   1.00   10.00    --   42.00  88.00 -77.81   27
 11  \w     13.00  40.00   1.00   10.00    --   46.00  83.00 -42.19   27
 12  \w     17.00  45.00   1.00   10.00    --   50.00  82.00 165.92   28
 13  \w     17.00  45.00   1.00   10.00    --   50.00  82.00  38.45   28
 14  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 150.00  100
 15  \w    -15.00  75.00   1.00   10.00    --   54.00 -57.00  60.00   90
 16  \w     24.00 124.00   1.00   10.00    --   54.00  77.00  90.00  100
 17  \w     24.00 124.00   1.00   10.00    --   54.00  77.00   0.00  100
 18  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 -90.00  100
 19  \w      1.00  96.00   1.00   10.00    --   54.00 -99.00 -30.00   95
 20  \w     23.00 111.00   1.00   10.00    --   54.00-125.00-120.00   88
 21  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 120.00  100
 22  \w     24.00 124.00   1.00   10.00    --   54.00  77.00 -60.00  100
 23  \w     24.00 124.00   1.00   10.00    --   54.00  77.00-120.00  100
 24  \w     23.00 111.00   1.00   10.00    --   54.00-125.00 -60.00   88
 25  \w     24.00 124.00   1.00   10.00    --   54.00  77.00-150.00  100
 26  \w     34.00 126.00   1.00   10.00    --   58.00  67.00  81.54   92
 27  \w     29.00 128.00   1.00   10.00    --   58.00  76.00-173.72   99
 28  \w     29.00 128.00   1.00   10.00    --   58.00  75.00 -21.34   99
 29  \w     37.00 134.00   1.00   10.00    --   62.00  39.00 135.48   97
 30  \w     33.00 132.00   1.00   10.00    --   62.00  76.00 -80.30   99
 31  \w     37.00 136.00   1.00   10.00    --   66.00  76.00-136.16   99
 32  \w     38.00 135.00   1.00   10.00    --   66.00  73.00  53.73   97
 33  \w     39.00 135.00   1.00   10.00    --   66.00  72.00-163.00   96
 34  \w     42.00 140.00   1.00   10.00    --   70.00  74.00 -38.50   98
 35  \w     44.00 139.00   1.00   10.00    --   70.00  70.00  46.23   95
 36  \w     49.00 139.00   1.00   10.00    --   70.00  57.00-142.62   90
 37  \w     51.00 145.00   1.00   10.00    --   74.00  45.00  59.53   94
 38  \w     45.00 144.00   1.00   10.00    --   74.00  76.00 -65.04   99
 39  \w     52.00 142.00   1.00   10.00    --   74.00  61.00 -12.12   90
 40  \w     53.00 146.00   1.00   10.00    --   78.00  69.00 -66.01   93
 41  \w     54.00 146.00   1.00   10.00    --   78.00  67.00 106.32   92
 42  \w     50.00 148.00   1.00   10.00    --   78.00  74.00 140.76   98
 43  \w     64.00 156.00   1.00   20.00    --   86.00  50.00 131.10   92
 44  \w     57.00 100.00   1.00   20.00    --   86.00  76.00-150.13   43
 45  \w    133.00 169.00   1.00   20.00    --   98.00  44.00 147.36   36
 46  \w     80.00 127.00   1.00   20.00    --   98.00  44.00 147.36   47
 47  \w    134.00 160.00   1.00   20.00    --  108.00  64.00 -90.00   26
 48  \w     85.00 116.00   1.00   20.00    --  108.00  64.00 -90.00   31
 49  \w    132.00 158.00   1.00   20.00    --  108.00  77.00 120.00   26
 50  \w     78.00 104.00   1.00   20.00    --  108.00  77.00 120.00   26
 51  \w    111.00 178.00   1.00   20.00    --  108.00  77.00 -60.00   67
 52  \w     78.00 104.00   1.00   20.00    --  108.00  77.00 -60.00   26
 53  \w     86.00 177.00   1.00   20.00    --  108.00  48.00 -15.08   91
 54  \w     79.00 176.00   1.00   20.00    --  108.00  77.00-150.00   97
 55  \w     83.00 113.00   1.00   20.00    --  108.00-111.00   0.00   30
 56  \w    146.00 172.00   1.00   20.00    --  108.00  77.00   0.00   26
 57  \w     78.00 113.00   1.00   20.00    --  108.00  77.00   0.00   35
 58  \w     85.00 111.00   1.00   20.00    --  108.00  64.00  60.00   26
 59  \w     86.00 112.00   1.00   20.00    --  108.00  38.00 -30.00   26
 60  \w     82.00 157.00   1.00   20.00    --  108.00  38.00 -60.00   75
 61  \w     84.00 109.00   1.00   20.00    --  108.00  38.00-180.00   25
 62  \w     88.00 170.00   1.00   20.00    --  108.00  64.00  90.00   82
 63  \w     88.00 114.00   1.00   20.00    --  108.00  64.00 -30.00   26
 64  \w     79.00 105.00   1.00   20.00    --  108.00  77.00 -90.00   26
 65  \w    136.00 177.00   1.00   20.00    --  108.00  77.00 150.00   41
 66  \w     88.00 116.00   1.00   20.00    --  108.00  64.00 150.00   28
 67  \w     79.00 105.00   1.00   20.00    --  108.00  77.00 150.00   26
 68  \w     86.00 116.00   1.00   20.00    --  108.00  64.00 -60.00   30
 69  \w     42.00 109.00   1.00   20.00    --  108.00 -92.00-150.00   67
 70  \w     59.00 106.00   1.00   20.00    --  108.00-111.00 120.00   47
 71  \w     37.00  69.00   1.00   20.00    --  108.00 -92.00  60.00   32
 72  \w     86.00 112.00   1.00   20.00    --  108.00  64.00   0.00   26
 73  \w     85.00 142.00   1.00   20.00    --  108.00  64.00  30.00   57
 74  \w    117.00 178.00   1.00   20.00    --  108.00  77.00-120.00   61
 75  \w     81.00 106.00   1.00   20.00    --  108.00  77.00-120.00   25
 76  \w     93.00 124.00   1.00   20.00    --  108.00  50.00-180.00   31
 77  \w     79.00 137.00   1.00   20.00    --  108.00 -77.00-150.00   58
 78  \w     40.00  71.00   1.00   20.00    --  108.00 -77.00-150.00   31
 79  \w    124.00 177.00   1.00   20.00    --  108.00  77.00  60.00   53
 80  \w     79.00 157.00   1.00   20.00    --  108.00  77.00-180.00   78
 81  \w     78.00 104.00   1.00   20.00    --  108.00  77.00  60.00   26
 82  \w     82.00 108.00   1.00   20.00    --  108.00  77.00  90.00   26
 83  \w    122.00 176.00   1.00   20.00    --  108.00  77.00  30.00   54
 84  \w     88.00 115.00   1.00   20.00    --  108.00  64.00-120.00   27
 85  \w     78.00 104.00   1.00   20.00    --  108.00  77.00  30.00   26
 86  \w     83.00 120.00   1.00   20.00    --  108.00  38.00  90.00   37
 87  \w     78.00 104.00   1.00   20.00    --  108.00  77.00 -30.00   26
 88  \w     37.00 108.00   1.00   20.00    --  108.00 -92.00   0.00   71
 89  \w     38.00 108.00   1.00   20.00    --  108.00 -92.00 150.00   70
;
_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      0.0613145000
_diffrn_orient_matrix_UB_12      0.1535831000
_diffrn_orient_matrix_UB_13      -0.0444680000
_diffrn_orient_matrix_UB_21      -0.0573888000
_diffrn_orient_matrix_UB_22      0.0452573000
_diffrn_orient_matrix_UB_23      -0.1357860000
_diffrn_orient_matrix_UB_31      -0.1384266000
_diffrn_orient_matrix_UB_32      0.0695083000
_diffrn_orient_matrix_UB_33      0.0348555000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0271
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            23936
_diffrn_reflns_point_group_measured_fraction_full 0.929
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.030
_diffrn_reflns_theta_min         4.221
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.838
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.941
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.20a (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            bronze
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       irregular
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.116
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.116
_refine_diff_density_min         -0.149
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 2912 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     534
_refine_ls_number_reflns         6787
_refine_ls_number_restraints     121
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0271
_refine_ls_R_factor_gt           0.0256
_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^)+(0.0329P)^2^+0.1299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0618
_refine_ls_wR_factor_ref         0.0631
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.859
_reflns_Friedel_fraction_max     0.829
_reflns_number_gt                6573
_reflns_number_total             6787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc09111d2.cif
_cod_data_source_block           ga_vv35
_cod_depositor_comments
'Adding full bibliography for 7125679--7125681.cif.'
_cod_database_code               7125681
_audit_block_refno               3197
_audit_block_usercomment         'VV636, irregular, bronze'
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.921
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O5A-C51A \\sim O5A-C54A \\sim O5B-C51B \\sim O5B-C54B
 with sigma of 0.01
 C51A-C52A \\sim C53A-C54A \\sim C51B-C52B \\sim C53B-C54B
 with sigma of 0.01
 C52A-C53A \\sim C52B-C53B
 with sigma of 0.01
 C51A-C53A \\sim C54A-C52A \\sim C51B-C53B \\sim C54B-C52B
 with sigma of 0.02
 O5A-C52A \\sim O5B-C52B \\sim O5A-C53A \\sim O5B-C53B
 with sigma of 0.02
 Mg-O5A \\sim Mg-O5B \\sim Mg-O4
 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 C31 \\sim C32 \\sim C33 \\sim C34
\\sim C35 \\sim C36 \\sim C37 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim
C51A \\sim C52A \\sim C53A \\sim C54A \\sim C51B \\sim C52B \\sim C53B \\sim
C54B \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5A \\sim O5B: within 1A with
sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O5A, C51A, C52A, C53A, C54A, O5B, C51B, C52B, C53B, C54B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O5B)=Sof(C51B)=Sof(H51C)=Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=
 Sof(C53B)=Sof(H53C)=Sof(H53D)=Sof(C54B)=Sof(H54C)=Sof(H54D)=1-FVAR(1)
 Sof(O5A)=Sof(C51A)=Sof(H51A)=Sof(H51B)=Sof(C52A)=Sof(H52A)=Sof(H52B)=
 Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(C54A)=Sof(H54A)=Sof(H54B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C16(H16), C29(H29)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C15(H15A,H15B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B), C51A(H51A,H51B), C52A(H52A,H52B), C53A(H53A,H53B), C54A(H54A,
 H54B), C51B(H51C,H51D), C52B(H52C,H52D), C53B(H53C,H53D), C54B(H54C,H54D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C13(H13), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C32(H32), C33(H33), C35(H35), C36(H36)
6.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C)
;
_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 1.189
_oxdiff_exptl_absorpt_empirical_full_min 0.855
_shelx_res_checksum              47635
_cell_oxdiff_length_a            9.5675(4)
_cell_oxdiff_length_b            9.7347(4)
_cell_oxdiff_length_c            11.4970(3)
_cell_oxdiff_angle_alpha         65.664(3)
_cell_oxdiff_angle_beta          88.065(3)
_cell_oxdiff_angle_gamma         84.019(3)
_cell_oxdiff_volume              970.28(6)
_cell_oxdiff_measurement_reflns_used 16003