Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using Biomimetic Diels-Alder Reactions of Double Diene Precursors.
Larson, Reed T.; Pemberton, Ryan P.; Franke, Jenna M.; Tantillo, Dean J.; Thomson, Regan J.; Journal of the American Chemical Society 137 (2015) 11197–11204; doi:10.1021/jacs.5b07710

data_4124295
_publ_section_title
;
 Total Synthesis of the Galbulimima Alkaloids Himandravine and GB17 Using
 Biomimetic Diels-Alder Reactions of Double Diene Precursors.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11197
_journal_page_last               11204
_journal_paper_doi               10.1021/jacs.5b07710
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H32 N O2, Cl'
_chemical_formula_sum            'C21 H32 Cl N O2'
_chemical_formula_weight         365.92
_space_group_crystal_system      hexagonal
_space_group_IT_number           173
_space_group_name_Hall           'P 6c'
_space_group_name_H-M_alt        'P 63'
_symmetry_space_group_name_Hall  'P 6c'
_symmetry_space_group_name_H-M   'P 63'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2014-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.3539(6)
_cell_length_b                   22.3539(6)
_cell_length_c                   7.4198(2)
_cell_measurement_reflns_used    9314
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.012
_cell_measurement_theta_min      3.955
_cell_volume                     3210.92(15)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.98
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.949
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 0.949
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            22424
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.031
_diffrn_reflns_theta_min         2.282
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.669
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6313
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0601 before and 0.0359 after correction.
The Ratio of minimum to maximum transmission is 0.8388.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.135
_exptl_crystal_description       plate
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.428
_exptl_crystal_size_mid          0.302
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.123
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1637 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.010(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3645
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0229
_refine_ls_R_factor_gt           0.0228
_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^)+(0.0364P)^2^+0.5754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0615
_refine_ls_wR_factor_ref         0.0616
_reflns_Friedel_coverage         0.829
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                3620
_reflns_number_total             3645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b07710_si_004.cif
_cod_data_source_block           n3323
_cod_depositor_comments
'Adding full bibliography for 4124293--4124295.cif.'
_cod_original_cell_volume        3210.92(19)
_cod_database_code               4124295
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.812
_shelx_estimated_absorpt_t_min   0.535
_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:
 C2(H2), C6(H6), C10(H10), C15(H15), C16(H16), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,
 H12B), C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C20(H20)
2.d Idealised Me refined as rotating group:
 C1(H1C,H1D,H1E), C21(H21A,H21B,H21C)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 351.1 Ang^3^ [10.9%]
Total electron count / cell = 69.7
;
_shelx_res_checksum              2913
_shelx_hkl_checksum              32778
_olex2_submission_special_instructions 'No special instructions were received'