Catalytic Asymmetric Intra- and Intermolecular Haloetherification of Enones: An Efficient Approach to (−)-Centrolobine
Zhou, Pengfei; Cai, Yunfei; Zhong, Xia; Luo, Weiwei; Kang, Tengfei; Li, Jun; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming; ACS Catalysis 6 (2016) 7778–; doi:10.1021/acscatal.6b02048

data_4513976
_publ_section_title
;
 Catalytic Asymmetric Intra- and Intermolecular Haloetherification of
 Enones: An Efficient Approach to (&#x2212;)-Centrolobine
;
_journal_issue                   11
_journal_name_full               'ACS Catalysis'
_journal_page_first              7778
_journal_paper_doi               10.1021/acscatal.6b02048
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C20 H21 Br O2'
_chemical_formula_sum            'C20 H21 Br O2'
_chemical_formula_weight         373.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-06
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.410(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.4678(5)
_cell_length_b                   8.6283(4)
_cell_length_c                   18.6625(10)
_cell_measurement_reflns_used    2186
_cell_measurement_temperature    269.85(10)
_cell_measurement_theta_max      24.2750
_cell_measurement_theta_min      4.0260
_cell_volume                     880.19(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      269.85(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -12.00   90.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -       19.1862   77.0000  150.0000 102

  2 omega  -12.00   90.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -       19.1862   77.0000   60.0000 102

  3 omega  -12.00   90.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -       19.1862   77.0000  -60.0000 102

  4 omega  -12.00   90.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -       19.1862   77.0000   30.0000 102

  5 omega  -12.00   90.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -       19.1862   77.0000  -90.0000 102

  6 omega  -52.00   51.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -      -20.1237   77.0000 -120.0000 103

  7 omega  -28.00   49.00   1.0000    8.1400
omega____ theta____ kappa____ phi______ frames
    -      -20.1237   77.0000   60.0000 77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0112856000
_diffrn_orient_matrix_UB_12      -0.0481499000
_diffrn_orient_matrix_UB_13      0.0305542000
_diffrn_orient_matrix_UB_21      0.0160771000
_diffrn_orient_matrix_UB_22      0.0654312000
_diffrn_orient_matrix_UB_23      0.0226221000
_diffrn_orient_matrix_UB_31      -0.1282863000
_diffrn_orient_matrix_UB_32      0.0123863000
_diffrn_orient_matrix_UB_33      -0.0007735000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0491
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            10789
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.364
_diffrn_reflns_theta_min         3.728
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64080
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description
;
;
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.414
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 836 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         3601
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0469P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0963
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.873
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2469
_reflns_number_total             3601
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b02048_si_004.cif
_cod_data_source_block           fxm-zpf-0706
_cod_depositor_comments
'Adding full bibliography for 4513975--4513977.cif.'
_cod_original_cell_volume        880.20(10)
_cod_database_code               4513976
_reflns_odcompleteness_completeness 99.69
_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
2.a Ternary CH refined with riding coordinates:
 C007(H007), C00G(H00J)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00D,H00E), C00E(H00F,H00G), C00F(H00H,H00I), C00I(H00L,H00M), C00J(H00N,
 H00O)
2.c Aromatic/amide H refined with riding coordinates:
 C008(H008), C00A(H00A), C00B(H00B), C00C(H00C), C00H(H00K), C00K(H00P),
 C00L(H00Q), C00M(H00R), C00N(H00S)
;
_shelx_res_checksum              49056
_shelx_hkl_checksum              28952
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-07-06
_olex2_submission_special_instructions 'No special instructions were received'