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_4515684
_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
'8(F1.5 Sb0.25), C H2 Cl2, 2(C57 H53 F12 N3 O4 P)'
_chemical_formula_sum            'C115 H108 Cl2 F36 N6 O8 P2 Sb2'
_chemical_formula_weight         2762.41
_space_group_crystal_system      tetragonal
_space_group_IT_number           90
_space_group_name_Hall           'P 4ab 2ab'
_space_group_name_H-M_alt        'P 4 21 2'
_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            8
_cell_length_a                   23.1560(8)
_cell_length_b                   23.1560(8)
_cell_length_c                   45.3164(15)
_cell_measurement_reflns_used    9705
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.503
_cell_measurement_theta_min      2.384
_cell_volume                     24298.7(14)
_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      99.98
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       64
_diffrn_reflns_limit_l_min       -64
_diffrn_reflns_number            180867
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.599
_diffrn_reflns_theta_min         2.162
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3928
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0716 before and 0.0559 after correction.
The Ratio of minimum to maximum transmission is 0.9072.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.510
_exptl_crystal_description       block
_exptl_crystal_F_000             11152
_exptl_crystal_size_max          0.282
_exptl_crystal_size_mid          0.268
_exptl_crystal_size_min          0.247
_refine_diff_density_max         1.951
_refine_diff_density_min         -1.261
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Flack x determined using 12896 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.024(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1671
_refine_ls_number_reflns         37346
_refine_ls_number_restraints     92
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0538
_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^)+(0.0590P)^2^+35.8909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1398
_refine_ls_wR_factor_ref         0.1455
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                32709
_reflns_number_total             37346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01374_si_006.cif
_cod_data_source_block           mo_0260_cg_0m_sq
_cod_original_cell_volume        24298.7(19)
_cod_database_code               4515684
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.861
_shelx_estimated_absorpt_t_min   0.843
_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. Restrained distances
 F39B-C207
 1.41 with sigma of 0.02
 F38B-C207 = F37B-C207
 1.41 with sigma of 0.02
 C107-F37A
 1.41 with sigma of 0.02
 F38A-C107 = F39A-C107
 1.41 with sigma of 0.02
 F29B-F30B
 2.14 with sigma of 0.02
 F29B-C57B
 1.41 with sigma of 0.02
 F30B-C57B
 1.41 with sigma of 0.02
 F30A-C57A
 1.41 with sigma of 0.02
 F28A-C57A
 1.41 with sigma of 0.02
 F30A-F28A
 2.14 with sigma of 0.02
 F30B-F28B
 2.14 with sigma of 0.02
 F28B-F29B
 2.14 with sigma of 0.02
 F28B-C57B
 1.41 with sigma of 0.02
 F29A-C57A
 1.41 with sigma of 0.02
 F30A-F29A
 2.14 with sigma of 0.02
 F28A-F29A
 2.14 with sigma of 0.02
 Cl1-C115 = Cl2-C115
 1.76 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C57A, F29A, F28A, F30A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C57B, F28B, F30B, F29B
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 F37A, F38A, F39A, C107
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F37B, F38B, F39B, C207
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F37B)=Sof(F38B)=Sof(F39B)=Sof(C205)=Sof(H205)=Sof(C204)=Sof(C203)=
 Sof(H203)=Sof(C202)=Sof(H202)=Sof(C201)=Sof(C206)=Sof(H206)=Sof(C207)=1-FVAR(1)
 Sof(F37A)=Sof(F38A)=Sof(F39A)=Sof(C105)=Sof(H105)=Sof(C104)=Sof(C103)=
 Sof(H103)=Sof(C102)=Sof(H102)=Sof(C101)=Sof(C106)=Sof(H106)=Sof(C107)=FVAR(1)
 Sof(F28B)=Sof(F29B)=Sof(F30B)=Sof(C57B)=1-FVAR(2)
 Sof(F28A)=Sof(F29A)=Sof(F30A)=Sof(C57A)=FVAR(2)
5.a Free rotating group:
 Cl2(Cl1,C115)
5.b Ternary CH refined with riding coordinates:
 C21(H21), C25(H25), C26(H26), C78(H78), C82(H82), C83(H83)
5.c Secondary CH2 refined with riding coordinates:
 C115(H11D,H11E)
5.d 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), C45(H45), C46(H46), C48(H48), C49(H49),
  C52(H52), C53(H53), C55(H55), C56(H56), C62(H62), C64(H64), C71(H71),
 C73(H73), C86(H86), C87(H87), C89(H89), C90(H90), C93(H93), C94(H94), C96(H96),
  C97(H97), C105(H105), C103(H103), C102(H102), C106(H106), C109(H109),
 C110(H110), C112(H112), C113(H113), C205(H205), C203(H203), C202(H202),
 C206(H206)
5.e Fitted hexagon refined as free rotating group:
 C105(C104,C103,C102,C101,C106), C205(C204,C203,C202,C201,C206)
5.f Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10D,H10E,H10F), C11(H11A,H11B,H11C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C66(H66A,H66B,H66C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C99(H99A,
 H99B,H99C), C100(H10A,H10B,H10C)
;
_shelx_res_checksum              13206
_shelx_hkl_checksum              34701
_shelx_fab_checksum              73165
_olex2_exptl_crystal_mounting_method
'Long axis, measured with large detector distance (70 mm). Minor twinning observed, but could not be resolved due to very small extent of second domain.'
_olex2_submission_special_instructions 'No special instructions were received'