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_4515689
_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         'F6 Sb, C H2 Cl2, C63 H57 F12 N3 O4 P'
_chemical_formula_sum            'C64 H59 Cl2 F18 N3 O4 P Sb'
_chemical_formula_weight         1499.76
_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'
_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                 98.349(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2724(11)
_cell_length_b                   25.712(2)
_cell_length_c                   22.718(2)
_cell_measurement_reflns_used    5634
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.242
_cell_measurement_theta_min      2.292
_cell_volume                     6514.7(10)
_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      99.99
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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  0.0590
_diffrn_reflns_av_unetI/netI     0.0749
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            90698
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.089
_diffrn_reflns_theta_min         2.294
_exptl_absorpt_coefficient_mu    0.631
_exptl_absorpt_correction_T_max  0.4143
_exptl_absorpt_correction_T_min  0.3268
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1380 before and 0.0603 after correction.
The Ratio of minimum to maximum transmission is 0.7888.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_description       plate
_exptl_crystal_F_000             3032
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.501
_refine_diff_density_min         -1.314
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 8032 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1803
_refine_ls_number_reflns         31219
_refine_ls_number_restraints     94
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0964
_refine_ls_R_factor_gt           0.0634
_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^)+(0.0782P)^2^+6.0525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1463
_refine_ls_wR_factor_ref         0.1638
_reflns_Friedel_coverage         0.949
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                22224
_reflns_number_total             31219
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01374_si_005.cif
_cod_data_source_block           mo_0270_cg_0m
_cod_original_cell_volume        6514.6(11)
_cod_database_code               4515689
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.884
_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 planarity
 C75B, C76B, C77B, C78B, C79B, C80B, C81B, C82B, C83B
 with sigma of 0.1
 C75A, C76A, C77A, C78A, C79A, C80A, C81A, C82A, C83A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(C64B) = Uanis(C64A)
Uanis(N4B) = Uanis(N4A)
Uanis(C65B) = Uanis(C65A)
Uanis(N6B) = Uanis(N6A)
Uanis(N5A) = Uanis(N5B)
Uanis(C65A) = Uanis(N4B)
Uanis(C65B) = Uanis(N4A)
4. Rigid body (RIGU) restrains
 Cl3, C2L, Cl4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19, F20, F21, C126
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82B, C78B, C79B, C80B, C75B, C76B, C77B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl8, C4L, Cl7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl4, C2L, Cl3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Cl3)=Sof(Cl4)=Sof(C2L)=Sof(HB)=Sof(HC)=Sof(Cl7)=Sof(Cl8)=Sof(C4L)=
 Sof(H4LA)=Sof(H4LB)=Sof(N4B)=Sof(N5B)=Sof(N6B)=Sof(C65B)=Sof(C64B)=Sof(C78B)=
 Sof(C77B)=Sof(H9EA)=Sof(C76B)=Sof(C75B)=Sof(C80B)=Sof(C79B)=Sof(H0FA)=
 Sof(C81B)=Sof(H4FA)=Sof(H5FA)=Sof(H6FA)=Sof(C82B)=Sof(H0GA)=Sof(H1GA)=
 Sof(H2GA)=Sof(C83B)=Sof(H6GA)=Sof(H7GA)=Sof(H8GA)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C1L)=Sof(H)=Sof(HA)=Sof(Cl5)=Sof(Cl6)=Sof(C3L)=Sof(HD)=
 Sof(HE)=Sof(N6A)=Sof(N5A)=Sof(N4A)=Sof(C64A)=Sof(C65A)=Sof(C78A)=Sof(C77A)=
 Sof(H7EA)=Sof(C76A)=Sof(C75A)=Sof(C80A)=Sof(C79A)=Sof(H8EA)=Sof(C81A)=
 Sof(H1FA)=Sof(H2FA)=Sof(H3FA)=Sof(C82A)=Sof(H7FA)=Sof(H8FA)=Sof(H9FA)=
 Sof(C83A)=Sof(H3GA)=Sof(H4GA)=Sof(H5GA)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C31(H2BA), C32(H3BA), C94(H0IA), C95(H1IA)
6.b Secondary CH2 refined with riding coordinates:
 C1L(H,HA), C2L(HB,HC), C3L(HD,HE), C4L(H4LA,H4LB)
6.c Aromatic/amide H refined with riding coordinates:
 C5(HF), C7(HG), C14(HQ), C16(HR), C23(H1AA), C25(H2AA), C35(H4BA), C36(H5BA),
 C38(H6BA), C39(H7BA), C42(H8BA), C43(H9BA), C45(H0CA), C46(H1CA), C51(H8CA),
 C52(H9CA), C54(H0DA), C55(H1DA), C58(H2DA), C59(H3DA), C61(H4DA), C62(H5DA),
 C68(H6DA), C70(H7DA), C77A(H7EA), C79A(H8EA), C77B(H9EA), C79B(H0FA),
 C86(H9GA), C88(H0HA), C98(H2IA), C99(H3IA), C101(H4IA), C102(H5IA), C105(H6IA),
  C106(H7IA), C108(H8IA), C109(H9IA), C114(H6JA), C115(H7JA), C117(H8JA),
 C118(H9JA), C121(H0KA), C122(H1KA), C124(H2KA), C125(H3KA)
6.d Fitted pentagon refined as free rotating group:
 N4B(N5B,N6B,C65B,C64B), N6A(N5A,N4A,C64A,C65A)
6.e Fitted hexagon refined as free rotating group:
 C78A(C77A,C76A,C75A,C80A,C79A), C78B(C77B,C76B,C75B,C80B,C79B)
6.f Idealised Me refined as rotating group:
 C9(HH,HI,HJ), C10(HK,HL,HM), C11(HN,HO,HP), C18(HS,HT,HU), C19(HV,HW,HX),
 C20(HY,HZ,H0AA), C27(H3AA,H4AA,H5AA), C28(H6AA,H7AA,H8AA), C29(H9AA,H0BA,H1BA),
  C48(H2CA,H3CA,H4CA), C49(H5CA,H6CA,H7CA), C72(H8DA,H9DA,H0EA), C73(H1EA,H2EA,
 H3EA), C74(H4EA,H5EA,H6EA), C81A(H1FA,H2FA,H3FA), C81B(H4FA,H5FA,H6FA),
 C82A(H7FA,H8FA,H9FA), C82B(H0GA,H1GA,H2GA), C83A(H3GA,H4GA,H5GA), C83B(H6GA,
 H7GA,H8GA), C90(H1HA,H2HA,H3HA), C91(H4HA,H5HA,H6HA), C92(H7HA,H8HA,H9HA),
 C111(H0JA,H1JA,H2JA), C112(H3JA,H4JA,H5JA)
;
_shelx_res_checksum              41036
_shelx_hkl_checksum              97920
_olex2_submission_special_instructions 'No special instructions were received'