Highly enantioselective desymmetrization of prochiral cyclic α,α-dicyanoalkenes via the direct vinylogous Michael/cyclization domino reaction
Mei, Hongjiang; Lin, Lili; Shen, Bin; Liu, Xiaohua; Feng, Xiaoming; Organic Chemistry Frontiers 5 (2018) 2505–; doi:10.1039/C8QO00545A

data_1554365
_publ_section_title
;
 Highly enantioselective desymmetrization of prochiral cyclic
 \a,\a-dicyanoalkenes via the direct vinylogous Michael/cyclization domino
 reaction
;
_journal_issue                   16
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              2505
_journal_paper_doi               10.1039/C8QO00545A
_journal_volume                  5
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H32 Br N3 O3'
_chemical_formula_sum            'C35 H32 Br N3 O3'
_chemical_formula_weight         622.54
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-05-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-05-16 deposited with the CCDC.
2018-07-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.568(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.6497(5)
_cell_length_b                   9.0221(2)
_cell_length_c                   14.1532(5)
_cell_measurement_reflns_used    8562
_cell_measurement_temperature    294.46(10)
_cell_measurement_theta_max      72.4600
_cell_measurement_theta_min      5.9560
_cell_volume                     1480.53(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)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.46(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -99.0000   90.0000 74

  2 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000    0.0000 84

  3 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   77.0000   30.0000 94

  4 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -57.0000   60.0000 84

  5 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000  -30.0000 67

  6 omega  -31.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -77.0000  -90.0000 94

  7 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  120.0000 84

  8 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921 -125.0000 -180.0000 67

  9 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000   60.0000 84

 10 omega   19.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   43.0000  -84.0000 86

 11 omega  -32.00   54.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921  -43.0000  123.0000 86

 12 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.2921   57.0000  -30.0000 84

 13 omega   81.00  176.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 95

 14 omega   81.00  176.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 95

 15 omega  100.00  178.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -180.0000 78

 16 omega   81.00  176.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 95

 17 omega   40.00   98.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 58

 18 omega   87.00  178.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -30.0000 91

 19 omega   88.00  116.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   60.0000 28

 20 omega  102.00  135.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  120.0000 33

 21 omega   88.00  117.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000    0.0000 29

 22 omega   91.00  116.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 25

 23 omega   89.00  171.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   90.0000 82

 24 omega   41.00   75.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  120.0000 34

 25 omega   92.00  118.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   60.0000 26

 26 omega   88.00  117.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 29

 27 omega   38.00   77.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 39

 28 omega   92.00  117.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   30.0000 25

 29 omega  122.00  175.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 53

 30 omega   81.00  107.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 26

 31 omega  126.00  176.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 50

 32 omega   62.00  109.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -60.0000 47

 33 omega   90.00  116.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 26

 34 omega   90.00  116.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 26

 35 omega   98.00  124.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000    0.0000 26

 36 omega   92.00  119.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 27

 37 omega   91.00  116.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 25

 38 omega   81.00  108.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 27

 39 omega   43.00   98.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 55

 40 omega   71.00   96.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   30.0000 25

 41 omega  123.00  178.00   1.0000    3.1100
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 55
;
_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      -0.1124084000
_diffrn_orient_matrix_UB_12      -0.0864956000
_diffrn_orient_matrix_UB_13      -0.0217707000
_diffrn_orient_matrix_UB_21      -0.0113083000
_diffrn_orient_matrix_UB_22      -0.0315784000
_diffrn_orient_matrix_UB_23      -0.1105759000
_diffrn_orient_matrix_UB_31      0.0700528000
_diffrn_orient_matrix_UB_32      -0.1437826000
_diffrn_orient_matrix_UB_33      0.0373173000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            16187
_diffrn_reflns_point_group_measured_fraction_full 0.963
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.764
_diffrn_reflns_theta_min         5.974
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.215
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62134
_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    1.396
_exptl_crystal_description       plate
_exptl_crystal_F_000             644
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.828
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Flack x determined using 2308 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         5547
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0894P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1157
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.922
_reflns_Friedel_fraction_max     0.886
_reflns_number_gt                5428
_reflns_number_total             5547
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00545a2.cif
_cod_data_source_block           fxm-mhj-2br
_cod_original_cell_volume        1480.52(9)
_cod_database_code               1554365
_reflns_odcompleteness_completeness 99.89
_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, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N006(H00A,H00B)
2.b Ternary CH refined with riding coordinates:
 C00P(H00P), C00T(H00T), C011(H011)
2.c Secondary CH2 refined with riding coordinates:
 C010(H01A,H01B), C015(H01F,H01G)
2.d Aromatic/amide H refined with riding coordinates:
 C00B(H00C), C00D(H00D), C00F(H00F), C00J(H00J), C00K(H00K), C00N(H00N),
 C00O(H00O), C00R(H00R), C00S(H00S), C00U(H00U), C00V(H00V), C00W(H00W),
 C00X(H00X), C012(H012)
2.e Idealised Me refined as rotating group:
 C00Y(H00E,H00G,H00H), C013(H01C,H01D,H01E), C016(H01H,H01I,H01J)
;
_shelx_res_checksum              2396
_shelx_hkl_checksum              17723
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-05-23
_olex2_submission_special_instructions 'No special instructions were received'