The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis
Pichon, Delphine; Soleilhavoup, Michele; Morvan, Jennifer; Junor, Glen P.; Vives, Thomas; Crévisy, Christophe; Lavallo, Vincent; Campagne, Jean-Marc; Mauduit, Marc; Jazzar, Rodolphe; Bertrand, Guy; Chemical Science  (2019) –; doi:10.1039/C9SC02810B

data_1552086
_publ_section_title
;
 The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in
 enantioselective catalysis
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02810B
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C44 H71 Cl Cu N, C2 H3 N'
_chemical_formula_sum            'C46 H74 Cl Cu N2'
_chemical_formula_weight         754.06
_chemical_name_systematic        CholestCAACCuCl
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-05-28
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-28 deposited with the CCDC.    2019-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.269(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2490(13)
_cell_length_b                   12.0899(15)
_cell_length_c                   17.740(2)
_cell_measurement_reflns_used    961
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      26.18
_cell_measurement_theta_min      2.60
_cell_volume                     2197.6(5)
_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  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.832
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0696
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.832
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13409
_diffrn_reflns_point_group_measured_fraction_full 0.766
_diffrn_reflns_point_group_measured_fraction_max 0.589
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         33.543
_diffrn_reflns_theta_min         5.188
_exptl_absorpt_coefficient_mu    0.589
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0536 before and 0.0447 after correction. The Ratio of minimum to maximum transmission is 0.8577. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.140
_exptl_crystal_description       plate
_exptl_crystal_F_000             820
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diethyl ether'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.496
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 2091 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.947
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         10194
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.947
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0160P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0695
_reflns_Friedel_coverage         0.362
_reflns_Friedel_fraction_full    0.530
_reflns_Friedel_fraction_max     0.326
_reflns_number_gt                8579
_reflns_number_total             10194
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02810b2.cif
_cod_data_source_block           cholescaaccucl
_cod_database_code               1552086
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.867
_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.a Ternary CH refined with riding coordinates:
 C8(H8), C12(H12), C15(H15), C16(H16), C19(H19), C27(H27), C30(H30), C37(H37),
 C41(H41)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C9(H9A,H9B), C10(H10A,H10B), C13(H13A,
 H13B), C14(H14A,H14B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B),
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B)
2.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C24(H24), C25(H25)
2.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C2A(H2AA,H2AB,H2AC)
;
_shelx_res_checksum              33275
_olex2_submission_special_instructions 'No special instructions were received'