Application of Electrocyclic Ring-Opening and Desymmetrizing Nucleophilic Trappings of meso-6,6-Dibromobicyclo[3.1.0]hexanes to Total Syntheses of Crinine and Haemanthamine Alkaloids.
Lan, Ping; Banwell, Martin G.; Willis, Anthony C.; The Journal of organic chemistry 84 (2019) 3431–3466; doi:10.1021/acs.joc.9b00018

data_4033914
_publ_section_title
;
 Application of Electrocyclic Ring-Opening and Desymmetrizing Nucleophilic
 Trappings of meso-6,6-Dibromobicyclo[3.1.0]hexanes to Total Syntheses of
 Crinine and Haemanthamine Alkaloids.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3431
_journal_page_last               3466
_journal_paper_doi               10.1021/acs.joc.9b00018
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_compound_source        local
_chemical_formula_moiety         'C8 H9 Br1 F3 N O'
_chemical_formula_sum            'C8 H9 Br F3 N O'
_chemical_formula_weight         272.06
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             12-06-29
_audit_creation_method           CRYSTALS_ver_14.11
_audit_update_record
;
2012-06-29- Report on C8 H9 Br F3 N O (Batch 2)
            by Anthony C. Willis
            for  Ping Lan and Martin Banwell

2012-07-02 - passes checkcif tests with few warnings

;
_cell_angle_alpha                101.537(6)
_cell_angle_beta                 91.971(9)
_cell_angle_gamma                107.637(8)
_cell_formula_units_Z            2
_cell_length_a                   5.0292(8)
_cell_length_b                   7.7369(11)
_cell_length_c                   13.795(2)
_cell_measurement_reflns_used    31532
_cell_measurement_temperature    200
_cell_measurement_theta_max      25
_cell_measurement_theta_min      3
_cell_volume                     498.60(13)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics
; 
ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997)
;
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      200
_diffrn_measured_fraction_theta_full 0.950
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       ' \f and \w scans with CCD '
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.078
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5313
_diffrn_reflns_theta_full        25.258
_diffrn_reflns_theta_max         25.258
_diffrn_reflns_theta_min         2.833
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.133
_exptl_absorpt_correction_T_max  0.69
_exptl_absorpt_correction_T_min  0.47
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.812
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             268
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.090
_refine_diff_density_max         2.98
_refine_diff_density_min         -1.94
_refine_ls_abs_structure_details 'Flack (1983), 1301 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.11(3)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9891
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3012
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.1109
_refine_ls_R_factor_gt           0.0947
_refine_ls_shift/su_max          0.049
_refine_ls_shift/su_mean         0.016
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.19P)^2^ + 0.86P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.2574
_refine_ls_wR_factor_gt          0.2388
_refine_ls_wR_factor_ref         0.2574
_reflns_limit_h_max              6
_reflns_limit_h_min              -5
_reflns_limit_k_max              9
_reflns_limit_k_min              -9
_reflns_limit_l_max              16
_reflns_limit_l_min              -16
_reflns_number_gt                2354
_reflns_number_total             3022
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   4.24
_oxford_diffrn_Wilson_scale      2.09
_oxford_refine_ls_r_factor_ref   0.1109
_oxford_refine_ls_scale          0.863(12)
_oxford_reflns_number_all        3012
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title '6271613 ban1224'
_cod_data_source_file            jo9b00018_si_010.cif
_cod_data_source_block           ban1224
_cod_original_cell_volume        498.61(13)
_cod_original_sg_symbol_H-M      'P 1 '
_cod_original_formula_sum        'C8 H9 Br1 F3 N O'
_cod_database_code               4033914
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
SUMFIX ELEMENT(1) ELEMENT(2) ELEMENT(3) 
FIX ELEMENT(4) 
RIDE N   (   7,X'S) H   (  71,X'S) 
RIDE N   (  27,X'S) H   ( 271,X'S) 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) H   (  32,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) H   (  42,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) H   (  52,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) H   ( 232,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) H   ( 242,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) H   ( 252,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;