Total Synthesis of (±)-Cephanolides B and C via a Palladium-Catalyzed Cascade Cyclization and Late-Stage sp<sup>3</sup> C-H Bond Oxidation.
Xu, Lun; Wang, Chao; Gao, Ziwei; Zhao, Yu-Ming; Journal of the American Chemical Society 140 (2018) 5653–5658; doi:10.1021/jacs.8b03015

data_4132353
_publ_section_title
;
 Total Synthesis of (+-)-Cephanolides B and C via a Palladium-Catalyzed
 Cascade Cyclization and Late-Stage sp<sup>3</sup> C-H Bond Oxidation.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5653
_journal_page_last               5658
_journal_paper_doi               10.1021/jacs.8b03015
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H25 I O3'
_chemical_formula_sum            'C19 H25 I O3'
_chemical_formula_weight         428.29
_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             2018-01-07
_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            4
_cell_length_a                   7.5257(10)
_cell_length_b                   13.6770(17)
_cell_length_c                   17.867(2)
_cell_measurement_reflns_used    9997
_cell_measurement_temperature    153
_cell_measurement_theta_max      68.552
_cell_measurement_theta_min      4.071
_cell_volume                     1839.0(4)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      153.01
_diffrn_measured_fraction_theta_full 0.999
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            23779
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.670
_diffrn_reflns_theta_min         4.070
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    13.776
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.2214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1534 before and 0.1042 after correction. The Ratio of minimum to maximum transmission is 0.2940. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.547
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         2.958
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.168
_refine_ls_abs_structure_details
;
 Flack x determined using 1360 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.459(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     212
_refine_ls_number_reflns         3384
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0587
_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^)+(0.0941P)^2^+4.9424P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1518
_refine_ls_wR_factor_ref         0.1522
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                3337
_reflns_number_total             3384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b03015_si_004.cif
_cod_data_source_block           s
_cod_database_code               4132353
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.104
_shelx_estimated_absorpt_t_min   0.055
_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:
 C00B(H00G), C00H(H00M), C00K(H00S)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00H,H00I), C00E(H00J,H00K), C00J(H00Q,H00R)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00G(H00L), C00L(H00T), C00N(H00X)
2.d Idealised Me refined as rotating group:
 C007(H00A,H00B,H00C), C008(H00D,H00E,H00F), C00I(H00N,H00O,H00P), C00M(H00U,
 H00V,H00W)
;
_shelx_res_checksum              90483
_shelx_hkl_checksum              58555
_olex2_submission_special_instructions 'No special instructions were received'