Chiral Cyclohexyl-Fused Spirobiindanes: Practical Synthesis, Ligand Development, and Asymmetric Catalysis.
Zheng, Zhiyao; Cao, Yuxi; Chong, Qinglei; Han, Zhaobin; Ding, Jiaming; Luo, Chenguang; Wang, Zheng; Zhu, Dongsheng; Zhou, Qi-Lin; Ding, Kuiling; Journal of the American Chemical Society 140 (2018) 10374–10381; doi:10.1021/jacs.8b07125

data_4132885
_publ_section_title
;
 Chiral Cyclohexyl-Fused Spirobiindanes: Practical Synthesis, Ligand
 Development, and Asymmetric Catalysis.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10374
_journal_page_last               10381
_journal_paper_doi               10.1021/jacs.8b07125
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C20 H19 O2, C6 H16 N, C20 H20 O2'
_chemical_formula_sum            'C46 H55 N O4'
_chemical_formula_weight         685.91
_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     direct
_audit_creation_date             2015-04-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1187(5)
_cell_length_b                   17.3795(11)
_cell_length_c                   26.7272(17)
_cell_measurement_reflns_used    9168
_cell_measurement_temperature    130
_cell_measurement_theta_max      29.90
_cell_measurement_theta_min      2.29
_cell_volume                     3771.2(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            38369
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.543
_diffrn_reflns_theta_min         1.524
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.076
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6907
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0629 before and 0.0487 after correction.
The Ratio of minimum to maximum transmission is 0.9257.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       block
_exptl_crystal_F_000             1480
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 3767 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4(4)
_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     470
_refine_ls_number_reflns         11517
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0622P)^2^+0.1862P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1125
_reflns_Friedel_coverage         0.798
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                9650
_reflns_number_total             11517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07125_si_004.cif
_cod_data_source_block           mo_dm15271_0m
_cod_database_code               4132885
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.981
_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.a Ternary CH refined with riding coordinates:
 C28(H28), C32(H32), C8(H8), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C33(H33A,H33B), C40(H40A,
 H40B), C41(H41A,H41B), C43(H43A,H43B), C45(H45A,H45B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C13(H13A,H13B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C23(H23), C24(H24), C36(H36), C37(H37), C38(H38), C2(H2A), C3(H3),
 C4(H4), C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4A), O1(H1), O2(H2)
;
_shelx_res_checksum              84692
_shelx_hkl_checksum              73385
_olex2_submission_special_instructions 'No special instructions were received'