Total Synthesis of Caesalpinnone A and Caesalpinflavan B: Evolution of a Concise Strategy.
Timmerman, Jacob C.; Sims, Noah J.; Wood, John L.; Journal of the American Chemical Society 141 (2019) 10082–10090; doi:10.1021/jacs.9b04472

data_4128292
_publ_section_title
;
 Total Synthesis of Caesalpinnone A and Caesalpinflavan B: Evolution of a
 Concise Strategy.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10082
_journal_page_last               10090
_journal_paper_doi               10.1021/jacs.9b04472
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C41 H38 O9'
_chemical_formula_sum            'C41 H38 O9'
_chemical_formula_weight         674.75
_chemical_name_common            SI-4
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                69.601(8)
_cell_angle_beta                 62.568(7)
_cell_angle_gamma                82.672(10)
_cell_formula_units_Z            2
_cell_length_a                   13.151(2)
_cell_length_b                   13.717(3)
_cell_length_c                   13.813(3)
_cell_measurement_reflns_used    9137
_cell_measurement_temperature    221(2)
_cell_measurement_theta_max      25.37
_cell_measurement_theta_min      2.40
_cell_volume                     2071.3(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      221.64
_diffrn_measured_fraction_theta_full 0.9254
_diffrn_measured_fraction_theta_max 0.9254
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            16128
_diffrn_reflns_theta_full        25.3702
_diffrn_reflns_theta_max         25.37
_diffrn_reflns_theta_min         2.40
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.076
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6595
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1043 before and 0.0464 after correction.
The Ratio of minimum to maximum transmission is 0.8850.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.0818
_exptl_crystal_description       block
_exptl_crystal_F_000             712.4128
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.183
_exptl_crystal_size_min          0.181
_refine_diff_density_max         2.2285
_refine_diff_density_min         -0.5615
_refine_diff_density_rms         0.1801
_refine_ls_d_res_high            0.8294
_refine_ls_d_res_low             8.4694
_refine_ls_goodness_of_fit_ref   2.0909
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    66
_refine_ls_number_parameters     460
_refine_ls_number_reflns         7044
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      2.0909
_refine_ls_R_factor_all          0.1848
_refine_ls_R_factor_gt           0.1648
_refine_ls_shift/su_max          1.8157
_refine_ls_shift/su_mean         0.1239
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4607
_refine_ls_wR_factor_ref         0.4883
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -13
_reflns_limit_k_max              16
_reflns_limit_k_min              -15
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                4974
_reflns_number_total             7044
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ja9b04472_si_002.cif
_cod_data_source_block           JLW_90_JT_2_0m
_cod_database_code               4128292
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H9ca,H5da,H6da} of C9ca, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups, {H3da,H3db,H3dc} of C3da, {H3ca,H3cb,H3cc} of C3ca
2.a Ternary CH refined with riding coordinates:
 C0ba(H0ba), C0ca(H0ca), C6aa(H6aa)
2.b Secondary CH2 refined with riding coordinates:
 C1ea(H1ea,H1eb), C2ca(H2ca,H2cb), C4ba(H4ba,H4bb), C7ca(H7ca,H7cb)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C1ba(H1ba), C1ca(H1ca), C1da(H1da), C2(H2), C3(H3), C4aa(H4aa),
 C4ca(H4ca), C4da(H4da), C5ca(H5ca), C6ba(H6ba), C7da(H7da), C8ba(H8ba),
 C8ca(H8ca), C8da(H8da), C9aa(H9aa), C9ba(H9ba), C9ca(H9ca)
2.d Idealised Me refined as rotating group:
 C3ca(H3ca,H3cb,H3cc), C3da(H3da,H3db,H3dc)
2.e Idealised tetrahedral OH refined as rotating group:
 O2aa(H2aa)
;
_olex2_submission_special_instructions 'No special instructions were received'