Biomimetic Total Synthesis of (±)-Griffipavixanthone via a Cationic Cycloaddition-Cyclization Cascade.
Reichl, Kyle D.; Smith, Michael J.; Song, Min K.; Johnson, Richard P.; Porco, Jr, John A; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b09265

data_4126513
_publ_section_title
;
 Biomimetic Total Synthesis of (+-)-Griffipavixanthone via a Cationic
 Cycloaddition-Cyclization Cascade.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b09265
_journal_year                    2017
_chemical_formula_moiety         'C H2 Cl2, 0.5(C42 H40 O12)'
_chemical_formula_sum            'C22 H22 Cl2 O6'
_chemical_formula_weight         453.29
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-12-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2016-12-08 # Formatted by publCIF

;
_cell_angle_alpha                87.710(2)
_cell_angle_beta                 74.122(2)
_cell_angle_gamma                76.856(2)
_cell_formula_units_Z            4
_cell_length_a                   10.2329(4)
_cell_length_b                   12.5402(5)
_cell_length_c                   17.1485(7)
_cell_measurement_reflns_used    9949
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.617
_cell_measurement_theta_min      2.679
_cell_volume                     2060.55(15)
_computing_cell_refinement       'SAINT (Bruker, 2006)'
_computing_data_collection       'APEX2 (Bruker, 2006)'
_computing_data_reduction        'SAINT (Bruker, 2006)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker Proteum-R'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  Montel
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0585
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            38248
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        66.721
_diffrn_reflns_theta_max         66.721
_diffrn_reflns_theta_min         2.680
_diffrn_source                   'rotating anode'
_exptl_absorpt_coefficient_mu    3.163
_exptl_absorpt_correction_T_max  0.8642
_exptl_absorpt_correction_T_min  0.7135
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2015)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.461
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.048
_refine_diff_density_max         0.433
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     585
_refine_ls_number_reflns         7190
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0471
_refine_ls_R_factor_gt           0.0430
_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^)+(0.0651P)^2^+1.2177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1221
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6428
_reflns_number_total             7190
_reflns_threshold_expression     'I > 2\s(I)'
_publcif_datablock.id            {8ac64df2-f6c7-4870-a6df-187a4c9f85f8}
_cod_data_source_file            ja7b09265_si_002.cif
_cod_data_source_block           reichl1_0m_all
_cod_original_cell_volume        2060.55(14)
_cod_database_code               4126513
_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. Restrained distances
 Cl2B-C1SB
 1.75 with sigma of 0.02
 Cl1S-C1SB
 1.75 with sigma of 0.02
 Cl4A-C2SA \\sim Cl3A-C2SA
 with sigma of 0.02
 Cl4A-C2SA \\sim Cl4B-C2SB
 with sigma of 0.02
 Cl4A-C2SA \\sim Cl3B-C2SB
 with sigma of 0.02
3. Rigid bond restraints
 Cl3A, Cl4A, C2SA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl3B, Cl4B, C2SB
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C2SA) = Uanis(C2SB)
5. Others
 Sof(Cl3B)=Sof(Cl4B)=Sof(C2SB)=Sof(H2SC)=Sof(H2SD)=Sof(Cl2B)=Sof(C1SB)=
 Sof(H1SC)=Sof(H1SD)=1-FVAR(1)
 Sof(Cl2A)=Sof(C1SA)=Sof(H1SA)=Sof(H1SB)=Sof(Cl3A)=Sof(Cl4A)=Sof(C2SA)=
 Sof(H2SA)=Sof(H2SB)=FVAR(1)
 Fixed Uiso: C1SB(0.03)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C26(H26)
6.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C1SA(H1SA,H1SB), C2SA(H2SA,H2SB), C2SB(H2SC,H2SD), C1SB(H1SC,
 H1SD)
6.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C40(H40), C13(H13), C37(H37), C28(H28), C7(H7), C25(H25), C3(H3)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C15(H15A,H15B,H15C), C39(H39A,H39B,H39C), C8(H8A,H8B,
 H8C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C42(H42A,H42B,H42C), C30(H30A,
 H30B,H30C), C1(H1A,H1B,H1C)
6.e Idealised tetrahedral OH refined as rotating group:
 O8(H8)
;
_shelx_res_checksum              22965
_shelx_hkl_checksum              82666
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'