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_7159384
_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 ad
_chemical_formula_moiety         'C61 H55 F N3 O4 Rh, 1[CH3COOC2H5]'
_chemical_formula_sum            'C65 H63 F N3 O6 Rh'
_chemical_formula_weight         1104.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-18
_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                 96.747(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.8510(17)
_cell_length_b                   15.3005(9)
_cell_length_c                   12.0037(7)
_cell_measurement_reflns_used    9811
_cell_measurement_temperature    100
_cell_measurement_theta_max      65.12
_cell_measurement_theta_min      3.08
_cell_volume                     5262.2(5)
_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
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0512
_diffrn_reflns_av_unetI/netI     0.0536
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            29351
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        65.166
_diffrn_reflns_theta_max         65.166
_diffrn_reflns_theta_min         3.085
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.119
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.5682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1054 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.7550.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.394
_exptl_crystal_description       plate
_exptl_crystal_F_000             2304
_exptl_crystal_size_max          0.132
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.013
_refine_diff_density_max         1.021
_refine_diff_density_min         -1.024
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Flack x determined using 3546 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     630
_refine_ls_number_reflns         8808
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0583
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0765P)^2^+21.9719P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1296
_refine_ls_wR_factor_ref         0.1340
_reflns_Friedel_coverage         0.887
_reflns_Friedel_fraction_full    0.962
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                8278
_reflns_number_total             8808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00735a2.cif
_cod_data_source_block           tius005
_cod_depositor_comments
'Adding full bibliography for 7159384--7159386.cif.'
_cod_database_code               7159384
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.684
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Others
 Fixed Y: Rh1(0.61356)
3.a Ternary CH refined with riding coordinates:
 C9(H9), C31(H31), C33(H33), C36(H36), C54(H54), C56(H56), C59(H59)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C30(H30A,H30B), C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B),
 C37(H37A,H37B), C38(H38A,H38B), C53(H53A,H53B), C55(H55A,H55B), C57(H57A,H57B),
  C58(H58A,H58B), C60(H60A,H60B), C61(H61A,H61B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C17(H17), C18(H18), C19(H19), C20(H20), C24(H24), C25(H25), C27(H27), C40(H40),
  C41(H41), C42(H42), C43(H43), C47(H47), C48(H48), C50(H50)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 168 electrons were 
found in a volume of 822\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[CH3COOC2H5] per Asymmetric Unit 
which account for 192 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              43084
_shelx_fab_checksum              49728
_olex2_submission_special_instructions 'No special instructions were received'