Neighboring Hydroxyl Group-Assisted Allylboration and Lewis Acid-Mediated Carbonyl-Ene Reaction for Access to a Hapalindole Cyclohexane Core with Multiple Contiguous Stereogenic Centers.
Li, Lu; Yang, Zhao; Yang, Jiao; Zhang, Quanzheng; Tan, Qiuyuan; Zhang, Changhui; Zhang, Min; The Journal of organic chemistry 84 (2019) 1605–1613; doi:10.1021/acs.joc.8b02712

data_4037548
_publ_section_title
;
 Neighboring Hydroxyl Group-Assisted Allylboration and Lewis Acid-Mediated
 Carbonyl-Ene Reaction for Access to a Hapalindole Cyclohexane Core with
 Multiple Contiguous Stereogenic Centers.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1605
_journal_page_last               1613
_journal_paper_doi               10.1021/acs.joc.8b02712
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C27 H30 Br N O4 S'
_chemical_formula_sum            'C27 H30 Br N O4 S'
_chemical_formula_weight         544.49
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-07-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.06.06 svn.r3414 for OlexSys, GUI svn.r5353)
;
_cell_angle_alpha                102.885(7)
_cell_angle_beta                 108.768(6)
_cell_angle_gamma                102.871(6)
_cell_formula_units_Z            2
_cell_length_a                   10.7773(6)
_cell_length_b                   11.0593(9)
_cell_length_c                   12.3513(11)
_cell_measurement_reflns_used    2738
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      26.1080
_cell_measurement_theta_min      3.8060
_cell_volume                     1287.7(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector_area_resol_mean 16.0892
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9176
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.369
_diffrn_reflns_theta_min         3.331
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    1.710
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32037
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.486
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.068
_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     326
_refine_ls_number_reflns         5271
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0942
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0475P)^2^+1.5592P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1305
_refine_ls_wR_factor_ref         0.1466
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3480
_reflns_number_total             5271
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02712_si_002.cif
_cod_data_source_block           ll
_cod_original_cell_volume        1287.75(18)
_cod_database_code               4037548
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 O4-H4 = O3-H3
 0.78 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C18(H18), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C22(H22A,H22B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C9(H9), C10(H10), C15(H15), C6(H6), C26(H26), C4(H4A), C7(H7),
 C0AA(H0AA)
3.d X=CH2 refined with riding coordinates:
 C27(H27A,H27B)
3.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C20(H20A,H20B,H20C), C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'