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_4037547
_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             2018-01-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.06.06 svn.r3414 for OlexSys, GUI svn.r5353)
;
_cell_angle_alpha                88.263(5)
_cell_angle_beta                 75.335(6)
_cell_angle_gamma                79.388(5)
_cell_formula_units_Z            2
_cell_length_a                   10.1855(7)
_cell_length_b                   10.7629(7)
_cell_length_c                   12.0612(8)
_cell_measurement_reflns_used    2601
_cell_measurement_temperature    292(2)
_cell_measurement_theta_max      27.6340
_cell_measurement_theta_min      3.9480
_cell_volume                     1257.08(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_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      292(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0892
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -55.00  60.00   1.00   16.50    --   18.38 -19.00 150.00  115
  2  \w     26.00  70.00   1.00   16.50    --   18.38-116.00-130.00   44
  3  \w    -20.00  57.00   1.00   16.50    --   18.38 -99.00 -30.00   77
  4  \w    -47.00  32.00   1.00   16.50    --   18.38 -57.00  90.00   79
  5  \w    -62.00   4.00   1.00   16.50    --  -18.54 -77.00  30.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0629729000
_diffrn_orient_matrix_UB_12      0.0425902000
_diffrn_orient_matrix_UB_13      0.0032614000
_diffrn_orient_matrix_UB_21      0.0200052000
_diffrn_orient_matrix_UB_22      0.0088239000
_diffrn_orient_matrix_UB_23      -0.0600352000
_diffrn_orient_matrix_UB_31      -0.0315329000
_diffrn_orient_matrix_UB_32      -0.0510406000
_diffrn_orient_matrix_UB_33      -0.0090280000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0935
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9227
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.382
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.752
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75744
_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    1.438
_exptl_crystal_description       Block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.38
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         5122
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1071
_refine_ls_R_factor_gt           0.0592
_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^)+(0.0565P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1291
_refine_ls_wR_factor_ref         0.1518
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3107
_reflns_number_total             5122
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02712_si_003.cif
_cod_data_source_block           20180119-zhangmin-ll-2
_cod_database_code               4037547
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C27 H30 Br N O4 S'
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 O4-H4
 0.82 with sigma of 0.01
 O4-H4
 0.82 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C24(H24), C23(H23)
3.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C21(H21A,H21B)
3.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C12(H12), C9(H9), C6(H6), C10(H10), C4(H4A), C7(H7), C19(H19),
 C3(H3A)
3.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C27(H27A,H27B,H27C), C1(H1A,H1B,H1C)
3.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_olex2_date_sample_data_collection 2018-01-19
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.576
_oxdiff_exptl_absorpt_empirical_full_min 0.412