Enantioconvergent synthesis of chiral fluorenols from racemic secondary alcohols <i>via</i> Pd(ii)/chiral norbornene cooperative catalysis.
Ding, Bo; Xue, Qilin; Wei, Han; Chen, Jiangwei; Liu, Ze-Shui; Cheng, Hong-Gang; Cong, Hengjiang; Tang, Jianting; Zhou, Qianghui; Chemical science 15 (2024) 7975–7981; doi:10.1039/d4sc01004c

data_1571491
_publ_section_title
;
 Enantioconvergent synthesis of chiral fluorenols from racemic secondary
 alcohols <i>via</i> Pd(ii)/chiral norbornene cooperative catalysis.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              7975
_journal_page_last               7981
_journal_paper_doi               10.1039/d4sc01004c
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H18 O2'
_chemical_formula_sum            'C17 H18 O2'
_chemical_formula_weight         254.31
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-30
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-01-03 deposited with the CCDC.	2024-04-18 downloaded from the CCDC.
;
_cell_angle_alpha                106.0410(10)
_cell_angle_beta                 106.0660(10)
_cell_angle_gamma                90.6580(10)
_cell_formula_units_Z            8
_cell_length_a                   12.20290(10)
_cell_length_b                   12.20700(10)
_cell_length_c                   20.2310(2)
_cell_measurement_reflns_used    54459
_cell_measurement_temperature    296.88(15)
_cell_measurement_theta_max      71.4800
_cell_measurement_theta_min      3.7200
_cell_volume                     2770.52(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.88(15)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.963
_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    -28.00  94.00   0.50    0.50    --    5.00  57.00 -90.00  244
  2  \w    -28.00  94.00   0.50    0.50    --    5.00  57.00-180.00  244
  3  \w    -86.00  42.00   0.50    0.50    --  -47.10  76.00  30.00  256
  4  \w   -136.00  -9.00   0.50    0.50    --  -47.10 -76.00-180.00  254
  5  \w   -136.00  -9.00   0.50    0.50    --  -47.10 -76.00 -30.00  254
  6  \w   -149.00 -22.00   0.50    0.50    --  -60.00 -76.00 101.53  254
  7  \w   -157.00 -30.00   0.50    0.50    --  -68.00 -76.00-136.64  254
  8  \w   -161.00 -34.00   0.50    0.50    --  -72.00 -76.00-163.94  254
  9  \w   -161.00 -34.00   0.50    0.50    --  -72.00 -76.00   1.98  254
 10  \w   -161.00 -34.00   0.50    0.50    --  -72.00 -76.00  64.42  254
 11  \w   -161.00 -34.00   0.50    0.50    --  -72.00 -76.00 -68.43  254
 12  \w   -161.00 -34.00   0.50    0.50    --  -72.00 -76.00 155.41  254
 13  \w   -169.00 -44.00   0.50    0.50    --  -80.00 -71.00 -29.23  250
 14  \w   -173.00 -46.00   0.50    0.50    --  -84.00 -74.00  61.92  254
 15  \w   -173.00 -47.00   0.50    0.50    --  -84.00 -72.00 154.91  252
 16  \w   -177.00 -51.00   0.50    0.50    --  -88.00 -73.00 -50.83  252
 17  \w   -177.00 -50.00   0.50    0.50    --  -88.00 -76.00 -71.15  254
 18  \w   -177.00 -50.00   0.50    0.50    --  -88.00 -76.00-127.53  254
 19  \w   -177.00 -51.00   0.50    0.50    --  -88.00 -73.00 134.54  252
 20  \w   -177.00 -50.00   0.50    0.50    --  -88.00 -76.00  50.94  254
 21  \w   -181.00 -55.00   0.50    0.50    --  -92.00 -73.00  17.59  252
 22  \w   -181.00 -54.00   0.50    0.50    --  -92.00 -75.00 120.25  254
 23  \w   -135.00  -7.00   0.50    0.50    --  -96.70  76.00-150.00  256
 24  \w   -186.00 -58.00   0.50    0.50    --  -96.70 -74.00  -1.44  256
 25  \w   -135.00  -7.00   0.50    0.50    --  -96.70  76.00  60.00  256
 26  \w   -135.00  -7.00   0.50    0.50    --  -96.70  76.00 -30.00  256
 27  \w   -186.00 -59.00   0.50    0.50    --  -96.70 -73.00  99.39  254
 28  \w   -186.00 -58.00   0.50    0.50    --  -96.70 -76.00-150.00  256
 29  \w   -135.00  -7.00   0.50    0.50    --  -96.70  76.00 -90.00  256
 30  \w   -186.00 -58.00   0.50    0.50    --  -96.70 -76.00 -90.00  256
 31  \w   -186.00 -58.00   0.50    0.50    --  -96.70 -75.00-173.96  256
 32  \w   -135.00  -7.00   0.50    0.50    --  -96.70  76.00 120.00  256
 33  \w    -28.00  94.00   0.50    0.50    --    5.00  57.00 -30.00  244
 34  \w   -136.00 -11.00   0.50    0.50    --  -47.10 -76.00  30.00  250
 35  \w   -136.00  -9.00   0.50    0.50    --  -47.10 -76.00 -90.00  254
 36  \w   -136.00  -9.00   0.50    0.50    --  -47.10 -76.00 -60.00  254
 37  \w   -153.00 -26.00   0.50    0.50    --  -64.00 -75.00  58.16  254
 38  \w   -157.00 -30.00   0.50    0.50    --  -68.00 -76.00 -98.90  254
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0323955000
_diffrn_orient_matrix_UB_12      -0.0628743000
_diffrn_orient_matrix_UB_13      0.0492790000
_diffrn_orient_matrix_UB_21      -0.0567894000
_diffrn_orient_matrix_UB_22      -0.1025688000
_diffrn_orient_matrix_UB_23      -0.0659553000
_diffrn_orient_matrix_UB_31      0.1146442000
_diffrn_orient_matrix_UB_32      -0.0541128000
_diffrn_orient_matrix_UB_33      0.0090260000
_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  0.0244
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            94592
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.398
_diffrn_reflns_theta_min         3.785
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52361
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.161
_refine_diff_density_min         -0.129
_refine_diff_density_rms         0.025
_refine_ls_abs_structure_details
;
 Flack x determined using 9253 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1454
_refine_ls_number_reflns         20130
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0580P)^2^+0.2553P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0885
_refine_ls_wR_factor_ref         0.0890
_reflns_Friedel_coverage         0.939
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.905
_reflns_number_gt                19660
_reflns_number_total             20130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01004c2.cif
_cod_data_source_block           zhouqh-dingbo-db-c-2-20231230-rt
_cod_depositor_comments
'Adding full bibliography for 1571490--1571491.cif.'
_cod_database_code               1571491
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'H C N O'
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.970
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C101(H101), C50(H50), C118(H118), C84(H84), C33(H33), C67(H67), C16(H16),
 C135(H135)
2.b Aromatic/amide H refined with riding coordinates:
 C92(H92), C55(H55), C93(H93), C37(H37), C35(H35), C8(H8), C103(H103),
 C43(H43), C71(H71), C129(H129), C127(H127), C24(H24), C69(H69), C88(H88),
 C110(H110), C25(H25), C128(H128), C2(H2A), C20(H20), C70(H70), C1(H1A),
 C53(H53), C10(H10), C36(H36), C109(H109), C9(H9), C54(H54), C41(H41), C78(H78),
  C42(H42), C105(H105), C111(H111), C94(H94), C3(H3), C26(H26), C62(H62),
 C120(H120), C122(H122), C18(H18), C60(H60), C104(H104), C76(H76), C121(H121),
 C77(H77), C61(H61), C87(H87), C19(H19), C86(H86)
2.c Idealised Me refined as rotating group:
 C100(H10B,H10C,H10D), C134(H13A,H13B,H13C), C117(H11A,H11B,H11C), C34(H34A,
 H34B,H34C), C17(H17A,H17B,H17C), C136(H13D,H13E,H13F), C85(H85A,H85B,H85C),
 C49(H49A,H49B,H49C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C102(H10E,H10F,
 H10G), C83(H83A,H83B,H83C), C116(H11D,H11E,H11F), C32(H32A,H32B,H32C),
 C51(H51A,H51B,H51C), C82(H82A,H82B,H82C), C15(H15A,H15B,H15C), C14(H14A,H14B,
 H14C), C133(H13G,H13H,H13I), C99(H99A,H99B,H99C), C119(H11G,H11H,H11I),
 C31(H31A,H31B,H31C), C65(H65A,H65B,H65C), C48(H48A,H48B,H48C)
;
_shelx_res_checksum              72943
_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 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.615