Anion-accelerated asymmetric Nazarov cyclization: access to vicinal all-carbon quaternary stereocenters.
Dickinson, Cody F.; Yap, Glenn P. A.; Tius, Marcus A.; Organic & biomolecular chemistry 21 (2023) 5014–5020; doi:10.1039/d3ob00735a

data_7159385
_publ_section_title
;
 Anion-accelerated asymmetric Nazarov cyclization: access to vicinal
 all-carbon quaternary stereocenters.
;
_journal_issue                   24
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5014
_journal_page_last               5020
_journal_paper_doi               10.1039/d3ob00735a
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C32 H40 O7'
_chemical_formula_sum            'C32 H40 O7'
_chemical_formula_weight         536.64
_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             2022-02-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-02-23 deposited with the CCDC.	2023-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.7321(2)
_cell_length_b                   9.8995(3)
_cell_length_c                   41.9029(12)
_cell_measurement_reflns_used    9269
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      64.80
_cell_measurement_theta_min      4.22
_cell_volume                     2792.59(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Venture Photon III'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            27183
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        65.012
_diffrn_reflns_theta_max         65.012
_diffrn_reflns_theta_min         2.109
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.721
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6268
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1409 before and 0.0623 after correction.
The Ratio of minimum to maximum transmission is 0.8328.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       needle
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.031
_exptl_crystal_size_min          0.029
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 1469 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     358
_refine_ls_number_reflns         4710
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.199
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0505
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0367P)^2^+1.2386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1025
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.707
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                4232
_reflns_number_total             4710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00735a2.cif
_cod_data_source_block           tius007
_cod_depositor_comments
'Adding full bibliography for 7159384--7159386.cif.'
_cod_database_code               7159385
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.898
_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:
 C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C16(H16A,H16B,H16C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              20240
_olex2_submission_special_instructions 'No special instructions were received'