Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids (+)-deethylibophyllidine and (+)-limaspermidine.
Du, Ji-Yuan; Zeng, Chao; Han, Xiao-Jie; Qu, Hu; Zhao, Xian-He; An, Xian-Tao; Fan, Chun-An; Journal of the American Chemical Society 137 (2015) 4267–4273; doi:10.1021/jacs.5b01926

data_4129402
_publ_section_title
;
 Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids
 (+)-deethylibophyllidine and (+)-limaspermidine.
;
_journal_issue                   12
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4267
_journal_page_last               4273
_journal_paper_doi               10.1021/jacs.5b01926
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration none
_chemical_formula_moiety         'C19 H26 N2 O'
_chemical_formula_sum            'C19 H26 N2 O'
_chemical_formula_weight         298.42
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.62594(9)
_cell_length_b                   13.76475(18)
_cell_length_c                   15.17422(18)
_cell_measurement_reflns_used    8176
_cell_measurement_temperature    293.8(2)
_cell_measurement_theta_max      70.6560
_cell_measurement_theta_min      3.1900
_cell_volume                     1592.83(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.8(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0230691000
_diffrn_orient_matrix_UB_12      -0.0384901000
_diffrn_orient_matrix_UB_13      0.0946376000
_diffrn_orient_matrix_UB_21      0.1997635000
_diffrn_orient_matrix_UB_22      0.0059393000
_diffrn_orient_matrix_UB_23      0.0142884000
_diffrn_orient_matrix_UB_31      -0.0197709000
_diffrn_orient_matrix_UB_32      0.1049003000
_diffrn_orient_matrix_UB_33      0.0338640000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11818
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         70.686
_diffrn_reflns_theta_min         5.832
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.596
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54684
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.124
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 1183 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.02(9)
_refine_ls_extinction_coef       0.0092(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     205
_refine_ls_number_reflns         3012
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0346
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0556P)^2^+0.1473P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.716
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                2919
_reflns_number_total             3012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01926_si_002.cif
_cod_data_source_block           dujy0328
_cod_database_code               4129402
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C12(H12A,H12B), C18(H18A,H18B), C17(H17A,H17B), C15(H15A,
 H15B), C16(H16A,H16B), C9(H9A,H9B), C19(H19A,H19B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C2(H2), C4(H4)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              10482
_shelx_hkl_checksum              20554