Enantioselective Total Synthesis of (-)-Caldaphnidine O via a Radical Cyclization Cascade.
Guo, Lian-Dong; Hu, Jingping; Zhang, Yan; Tu, Wentong; Zhang, Yue; Pu, Fan; Xu, Jing; Journal of the American Chemical Society 141 (2019) 13043–13048; doi:10.1021/jacs.9b07558

data_4127845
_publ_section_title
;
 Enantioselective Total Synthesis of (-)-Caldaphnidine O via a Radical
 Cyclization Cascade.
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13043
_journal_page_last               13048
_journal_paper_doi               10.1021/jacs.9b07558
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H41 N O4 S'
_chemical_formula_sum            'C32 H41 N O4 S'
_chemical_formula_weight         535.72
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4379(4)
_cell_length_b                   11.3975(5)
_cell_length_c                   28.3831(13)
_cell_measurement_reflns_used    9868
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.53
_cell_measurement_theta_min      2.29
_cell_volume                     2729.6(2)
_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      100.0
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'BrukerD8 venture microsource'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            22418
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.546
_diffrn_reflns_theta_min         2.292
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.158
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6940
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0783 before and 0.0518 after correction. The Ratio of minimum to maximum transmission is 0.9308. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.38
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 2351 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_coef       0.0068(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         6256
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0377P)^2^+0.7336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0749
_refine_ls_wR_factor_ref         0.0768
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                5808
_reflns_number_total             6256
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07558_si_003.cif
_cod_data_source_block           cxy0802_0m
_cod_database_code               4127845
_shelx_shelxl_version_number     2016/6
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C22(H22), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B), C23(H23A,H23B),
 C24(H24A,H24B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4A), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C19(H19),
 C20(H20), C31(H31), C32(H32)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C30(H30A,H30B,H30C)
2.e Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_olex2_submission_special_instructions 'No special instructions were received'