TADDOL-Derived Cationic Phosphonites: Toward an Effective Enantioselective Synthesis of [6]Helicenes via Au-Catalyzed Alkyne Hydroarylation
Nicholls, Leo D. M.; Marx, Maximilian; Hartung, Thierry; González-Fernández, Elisa; Golz, Christopher; Alcarazo, Manuel; ACS Catalysis 8 (2018) 6079–; doi:10.1021/acscatal.8b01374

data_4515686
_publ_section_title
;
 TADDOL-Derived Cationic Phosphonites: Toward an Effective
 Enantioselective Synthesis of [6]Helicenes via Au-Catalyzed Alkyne
 Hydroarylation
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              6079
_journal_paper_doi               10.1021/acscatal.8b01374
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C57 H53 Au Cl F12 N3 O4 P, F6 Sb'
_chemical_formula_sum            'C57 H53 Au Cl F18 N3 O4 P Sb'
_chemical_formula_weight         1571.16
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.6250(8)
_cell_length_b                   21.7951(18)
_cell_length_c                   24.924(2)
_cell_measurement_reflns_used    8737
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.399
_cell_measurement_theta_min      2.391
_cell_volume                     6314.9(8)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0607
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            47392
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.655
_diffrn_reflns_theta_min         2.396
_exptl_absorpt_coefficient_mu    2.914
_exptl_absorpt_correction_T_max  0.0523
_exptl_absorpt_correction_T_min  0.0157
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1278 before and 0.0768 after correction. The Ratio of minimum to maximum transmission is 0.3002. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.653
_exptl_crystal_description       plate
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.367
_exptl_crystal_size_mid          0.272
_exptl_crystal_size_min          0.032
_refine_diff_density_max         2.019
_refine_diff_density_min         -2.122
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Flack x determined using 5249 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     772
_refine_ls_number_reflns         17698
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0684
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0761P)^2^+9.0146P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1530
_refine_ls_wR_factor_ref         0.1626
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                13967
_reflns_number_total             17698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01374_si_009.cif
_cod_data_source_block           mo_0264_cg_0m_sq
_cod_original_cell_volume        6315.0(9)
_cod_database_code               4515686
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.414
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F8-F9
 2.14 with sigma of 0.02
 F9-F7
 2.14 with sigma of 0.02
 F8-F7
 2.14 with sigma of 0.02
 C50-C47
 1.48 with sigma of 0.02
 F9-C50
 1.41 with sigma of 0.02
 C50-F7
 1.41 with sigma of 0.02
 C50-F8
 1.41 with sigma of 0.02
3. Rigid bond restraints
 C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C47, C46, C48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C47: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C50 \\sim C46 \\sim C47 \\sim C48: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C49, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F7, F8, F9, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F1, C34, F2, F3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6.a Ternary CH refined with riding coordinates:
 C21(H21), C25(H25), C26(H26)
6.b Me refined with riding coordinates:
 C22(H22A,H22B,H22C)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C14(H14), C16(H16), C29(H29), C30(H30), C32(H32), C33(H33),
 C36(H36), C37(H37), C39(H39), C40(H40), C49(H49), C48(H48), C46(H46), C45(H45),
  C52(H52), C53(H53), C55(H55), C56(H56)
6.d Fitted hexagon refined as free rotating group:
 C44(C49,C48,C47,C46,C45)
6.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              41220
_shelx_hkl_checksum              48751
_shelx_fab_checksum              28883
_olex2_submission_special_instructions 'No special instructions were received'