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_4515692
_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
'C55 H46 Au Cl3 F12 N2 O4 P, F6 Sb, 1(C H2 Cl2)'
_chemical_formula_sum            'C56 H48 Au Cl5 F18 N2 O4 P Sb'
_chemical_formula_weight         1681.90
_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
_audit_creation_date             2018-03-29
_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                   11.8911(12)
_cell_length_b                   20.269(2)
_cell_length_c                   26.818(3)
_cell_measurement_reflns_used    6913
_cell_measurement_temperature    100.02
_cell_measurement_theta_max      32.59
_cell_measurement_theta_min      3.02
_cell_volume                     6463.7(12)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.02
_diffrn_detector_type            'PHOTON II area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'four-circle diffractometer'
_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_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            33061
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.507
_diffrn_reflns_theta_min         2.148
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.013
_exptl_absorpt_correction_T_max  0.6952
_exptl_absorpt_correction_T_min  0.6340
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1181 before and 0.0451 after correction.
The Ratio of minimum to maximum transmission is 0.9120.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.728
_exptl_crystal_description       plate
_exptl_crystal_F_000             3288
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.007
_refine_diff_density_min         -2.382
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Flack x determined using 7714 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0116(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         33061
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0439
_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^)+(0.0643P)^2^+5.6657P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1132
_refine_ls_wR_factor_ref         0.1173
_reflns_Friedel_coverage         0.840
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                29512
_reflns_number_total             33061
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01374_si_007.cif
_cod_data_source_block           mo_0048_cg_0m_4
_cod_original_cell_volume        6463.8(11)
_cod_database_code               4515692
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.570
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5395(11)
 0.4605(11)
2. 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
3. Restrained distances
 Cl5B-C56B = Cl4B-C56B = Cl4C-C56C = Cl5C-C56C
 1.8 with sigma of 0.02
 Cl4A-C56A = Cl5A-C56A
 1.8 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(F11) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C11B, F2B, F3B, F1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, C11A, F3A, F2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl5C, C56C, Cl4C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl5B, C56B, Cl4B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 F11, C34, F10, F12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C11B)=Sof(F2B)=Sof(F3B)=Sof(F1B)=1-FVAR(1)
 Sof(F1A)=Sof(C11A)=Sof(F3A)=Sof(F2A)=FVAR(1)
 Fixed Sof: Cl4A(0.33333) Cl4C(0.33333) Cl5A(0.33333) Cl5C(0.33333)
 C56A(0.33333) H56A(0.33333) H56B(0.33333) C56C(0.33333) H56C(0.33333)
 H56D(0.33333) Cl4B(0.33333) Cl5B(0.33333) C56B(0.33333) H56E(0.33333)
 H56F(0.33333)
7.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3)
7.b Secondary CH2 refined with riding coordinates:
 C56A(H56A,H56B), C56C(H56C,H56D), C56B(H56E,H56F)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C16(H16), C17(H17),
 C22(H22), C23(H23), C25(H25), C26(H26), C29(H29), C30(H30), C32(H32), C33(H33),
  C40(H40), C42(H42), C49(H49), C51(H51)
7.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C)
;
_shelx_res_checksum              58239
_shelx_hkl_checksum              76457
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'