Enantioselective Meerwein–Ponndorf–Verley reduction of β,γ-unsaturated α-keto esters by asymmetric binary-acid catalysis in the green solvent iPrOH
Qiu, Huixin; Ren, Jiayi; Zhang, Long; Song, Ran; Si, Wen; Yang, Daoshan; Wen, Lirong; Lv, Jian; Green Chemistry 25 (2023) 3948–3955; doi:10.1039/D2GC03441G

data_7246637
_publ_section_title
;
 Enantioselective Meerwein--Ponndorf--Verley reduction of
 \b,\g-unsaturated \a-keto esters by asymmetric binary-acid catalysis in
 the green solvent iPrOH
;
_journal_issue                   10
_journal_name_full               'Green Chemistry'
_journal_page_first              3948
_journal_page_last               3955
_journal_paper_doi               10.1039/D2GC03441G
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C13 H15 Br O3)'
_chemical_formula_sum            'C26 H30 Br2 O6'
_chemical_formula_weight         598.32
_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
_audit_creation_date             2021-08-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-30 deposited with the CCDC.	2023-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.5570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.17910(10)
_cell_length_b                   15.1836(2)
_cell_length_c                   14.4771(2)
_cell_measurement_reflns_used    12167
_cell_measurement_temperature    170.01(10)
_cell_measurement_theta_max      75.1580
_cell_measurement_theta_min      3.0300
_cell_volume                     1351.87(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.01(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 0.976
_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   -100.00 -66.00   0.50    0.05    --  -47.45 -80.00  25.00   68
  2  \w    -71.00  20.00   0.50    0.05    --  -47.45  80.00 149.00  182
  3  \w    -21.00  38.00   0.50    0.05    --   47.45 -80.00  25.00  118
  4  \w     41.00  71.00   0.50    0.05    --   47.45 -80.00  25.00   60
  5  \w   -133.00-107.00   0.50    0.05    --  -99.00 -80.00  25.00   52
  6  \w    108.00 135.00   0.50    0.05    --  103.25  80.00 149.00   54
  7  \w     33.00  79.00   0.50    0.05    --  103.25 -80.00  25.00   92
  8  \w   -113.00 -75.00   0.50    0.05    --  -47.45-125.00-180.00   76
  9  \w    -18.00   8.00   0.50    0.05    --  -47.45  19.00 120.00   52
 10  \w    -26.00   0.00   0.50    0.05    --  -47.45  38.00 -90.00   52
 11  \w   -120.00 -95.00   0.50    0.05    --  -47.45-125.00  30.00   50
 12  \w    -20.00  22.00   0.50    0.05    --  -47.45  19.00  90.00   84
 13  \w    -20.00  27.00   0.50    0.05    --  -47.45  19.00  30.00   94
 14  \w    -22.00  25.00   0.50    0.05    --  -47.45  19.00 150.00   94
 15  \w   -168.00 -97.00   0.50    0.05    --  -99.00 -30.00 120.00  142
 16  \w    -67.00 -30.00   0.50    0.05    --  -99.00  61.00  60.00   74
 17  \w   -166.00 -83.00   0.50    0.05    --  -99.00 -61.00  60.00  166
 18  \w   -140.00 -94.00   0.50    0.05    --  -99.00 -30.00 -90.00   92
 19  \w   -120.00 -94.00   0.50    0.05    --  -99.00 -77.00-120.00   52
 20  \w    -68.00 -43.00   0.50    0.05    --  -99.00  61.00 150.00   50
 21  \w    -99.00 -74.00   0.50    0.05    --  -99.00  80.00 149.00   50
 22  \w    -59.00 -34.00   0.50    0.05    --  -99.00  61.00 120.00   50
 23  \w   -168.00 -87.00   0.50    0.05    --  -99.00 -45.00  90.00  162
 24  \w   -168.00-122.00   0.50    0.05    --  -99.00 -77.00-120.00   92
 25  \w    100.00 167.00   0.50    0.05    --  103.25  30.00-180.00  134
 26  \w     32.00  71.00   0.50    0.05    --  103.25-125.00  90.00   78
 27  \w     70.00 108.00   0.50    0.05    --  103.25-125.00 120.00   76
 28  \w     33.00  63.00   0.50    0.05    --  103.25-125.00 120.00   60
 29  \w     35.00 108.00   0.50    0.05    --  103.25-125.00-180.00  146
 30  \w    114.00 152.00   0.50    0.05    --  103.25  45.00  60.00   76
 31  \w     31.00  57.00   0.50    0.05    --  103.25 -61.00-150.00   52
 32  \w     93.00 145.00   0.50    0.05    --  103.25  15.00 -90.00  104
 33  \w     33.00  96.00   0.50    0.05    --  103.25 -77.00  60.00  126
 34  \w     36.00  61.00   0.50    0.05    --  103.25 -61.00 -60.00   50
 35  \w     88.00 167.00   0.50    0.05    --  103.25  61.00 -90.00  158
 36  \w     81.00 108.00   0.50    0.05    --  103.25-125.00  90.00   54
 37  \w     92.00 168.00   0.50    0.05    --  103.25  45.00-150.00  152
 38  \w     38.00  73.00   0.50    0.05    --  103.25 -61.00-120.00   70
 39  \w     38.00  67.00   0.50    0.05    --  103.25-125.00 150.00   58
 40  \w    102.00 168.00   0.50    0.05    --  103.25  15.00 150.00  132
 41  \w     31.00  73.00   0.50    0.05    --  103.25 -61.00-180.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0025118000
_diffrn_orient_matrix_UB_12      0.0039977000
_diffrn_orient_matrix_UB_13      -0.1062323000
_diffrn_orient_matrix_UB_21      0.1285254000
_diffrn_orient_matrix_UB_22      0.0870717000
_diffrn_orient_matrix_UB_23      0.0094647000
_diffrn_orient_matrix_UB_31      0.2149410000
_diffrn_orient_matrix_UB_32      -0.0519516000
_diffrn_orient_matrix_UB_33      0.0076339000
_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  0.0318
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16499
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.203
_diffrn_reflns_theta_min         3.067
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.110
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44442
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.470
_exptl_crystal_description       plate
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.294
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2353 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         5343
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0530P)^2^+0.2498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.0872
_reflns_Friedel_coverage         0.886
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                5186
_reflns_number_total             5343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2gc03441g2.cif
_cod_data_source_block           tx7035a
_cod_depositor_comments          'Adding full bibliography for 7246637.cif.'
_cod_database_code               7246637
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOBr
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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) groups
2. Others
 Sof(H11B)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13B)=Sof(H13D)=
 Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C9(H9), C11(H11), C9A(H9A), C11A(H11A), C11A(H11B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C2A(H2A), C3A(H3A), C5A(H5A),
 C6A(H6A), C7A(H7A), C8A(H8A)
3.c Idealised Me refined as rotating group:
 C12(H12G,H12H,H12I), C13(H13G,H13H,H13I), C12A(H12A,H12B,H12C), C13A(H13A,
 H13B,H13C), C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F)
3.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1A(H1A)
;
_shelx_res_checksum              37998
_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 1.701
_oxdiff_exptl_absorpt_empirical_full_min 0.616