Stereodivergent Synthesis via Iridium-Catalyzed Asymmetric Double Allylic Alkylation of Cyanoacetate
Shen, Chong; Cheng, Xiang; Wei, Liang; Wang, Ruo-Qing; Wang, Chun-Jiang; Chemical Science  (2021) –; doi:10.1039/D1SC06115A

data_1565338
_publ_section_title
;
 Stereodivergent Synthesis via Iridium-Catalyzed Asymmetric Double Allylic
 Alkylation of Cyanoacetate
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC06115A
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H25 Br2 N O2'
_chemical_formula_sum            'C25 H25 Br2 N O2'
_chemical_formula_weight         531.28
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-11-24
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2021-07-14 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.4700(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.68950(10)
_cell_length_b                   11.14220(10)
_cell_length_c                   10.92190(10)
_cell_measurement_reflns_used    23537
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.4640
_cell_measurement_theta_min      3.9590
_cell_volume                     1202.09(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_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     34.00  89.00   0.50    0.50    --    0.00  32.00-142.00  110
  2  \w    -12.00  20.00   0.50    0.50    --    0.00  32.00-142.00   64
  3  \w     32.00  58.00   0.50    0.50    --   94.60 -32.00  58.00   52
  4  \w    107.00 146.00   0.50    0.50    --   94.60  32.00-142.00   78
  5  \w    -54.00 -16.00   0.50    0.50    --    0.00 -32.00  58.00   76
  6  \w    -12.00  13.00   0.50    0.50    --    0.00 -32.00  58.00   50
  7  \w     73.00 120.00   0.50    0.50    --   32.00  72.00 -45.98   94
  8  \w      6.00  47.00   0.50    0.50    --   32.00  72.00 -45.98   82
  9  \w     10.00  61.00   0.50    0.50    --   36.00  72.00 170.83  102
 10  \w      1.00  61.00   0.50    0.50    --   44.00 -38.00 -16.74  120
 11  \w    -44.00  -3.00   0.50    0.50    --   44.00 -38.00 -16.74   82
 12  \w     29.00  54.00   0.50    0.50    --   52.00  73.00-118.99   50
 13  \w     25.00  83.00   0.50    0.50    --   52.00  72.00  24.57  116
 14  \w     32.00  79.00   0.50    0.50    --   60.00  75.00 -69.87   94
 15  \w     36.00  61.00   0.50    0.50    --   64.00  74.00 -35.59   50
 16  \w     37.00  73.00   0.50    0.50    --   64.00  75.00  69.04   72
 17  \w     36.00  67.00   0.50    0.50    --   64.00  75.00 178.18   62
 18  \w     41.00  75.00   0.50    0.50    --   68.00  75.00-114.22   68
 19  \w     40.00  65.00   0.50    0.50    --   68.00  74.00 135.23   50
 20  \w     40.00  77.00   0.50    0.50    --   68.00  74.00  35.97   74
 21  \w     41.00  69.00   0.50    0.50    --   68.00  75.00 -19.38   56
 22  \w     40.00  72.00   0.50    0.50    --   68.00  75.00-151.53   64
 23  \w     44.00  69.00   0.50    0.50    --   72.00  75.00  89.21   50
 24  \w     45.00  73.00   0.50    0.50    --   72.00  75.00 105.88   56
 25  \w    126.00 157.00   0.50    0.50    --   72.00  74.00 -41.94   62
 26  \w     46.00  71.00   0.50    0.50    --   72.00  74.00 -41.94   50
 27  \w    100.00 165.00   0.50    0.50    --   76.00  75.00   1.94  130
 28  \w     49.00  76.00   0.50    0.50    --   76.00  75.00   1.94   54
 29  \w     61.00 107.00   0.50    0.50    --   84.00  67.00 158.60   92
 30  \w    136.00 172.00   0.50    0.50    --   94.60  61.00 120.00   72
 31  \w     73.00  99.00   0.50    0.50    --   94.60 -77.00 -90.00   52
 32  \w      5.00  69.00   0.50    0.50    --   94.60 -77.00 -90.00  128
 33  \w     71.00 128.00   0.50    0.50    --   94.60  61.00 120.00  114
 34  \w      7.00  36.00   0.50    0.50    --   94.60 -82.00 150.00   58
 35  \w      5.00  39.00   0.50    0.50    --   94.60 -82.00-150.00   68
 36  \w     73.00 164.00   0.50    0.50    --   94.60  58.00 -59.67  182
 37  \w     67.00 183.00   0.50    0.50    --   94.60  72.00-104.35  232
 38  \w     98.00 126.00   0.50    0.50    --   94.60 -82.00   0.00   56
 39  \w     71.00 182.00   0.50    0.50    --   94.60  61.00  60.00  222
 40  \w      8.00 125.00   0.50    0.50    --   94.60 -82.00 -30.00  234
 41  \w     74.00 125.00   0.50    0.50    --   94.60 -82.00  60.00  102
 42  \w     72.00 115.00   0.50    0.50    --   94.60  61.00   0.00   86
 43  \w     63.00 109.00   0.50    0.50    --   94.60 -61.00 150.00   92
 44  \w     30.00  56.00   0.50    0.50    --   94.60 -61.00 150.00   52
 45  \w     71.00 169.00   0.50    0.50    --   94.60  59.00-123.34  196
 46  \w    127.00 152.00   0.50    0.50    --   94.60  61.00  90.00   50
 47  \w     74.00 112.00   0.50    0.50    --   94.60  61.00  90.00   76
 48  \w     78.00 154.00   0.50    0.50    --   94.60  30.00  30.00  152
 49  \w     71.00 168.00   0.50    0.50    --   94.60  61.00-150.00  194
 50  \w     42.00  68.00   0.50    0.50    --   94.60 -82.00  60.00   52
 51  \w     80.00 113.00   0.50    0.50    --   94.60  77.00 -60.00   66
 52  \w      5.00  94.00   0.50    0.50    --   94.60 -82.00   0.00  178
 53  \w     73.00 178.00   0.50    0.50    --   94.60  61.00-180.00  210
 54  \w     72.00 121.00   0.50    0.50    --   94.60  56.00 151.60   98
 55  \w     71.00 117.00   0.50    0.50    --   94.60  61.00  30.00   92
 56  \w     42.00 122.00   0.50    0.50    --   94.60 -82.00 150.00  160
 57  \w     93.00 120.00   0.50    0.50    --   94.60 -82.00-150.00   54
 58  \w    151.00 176.00   0.50    0.50    --   94.60  61.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1276797000
_diffrn_orient_matrix_UB_12      -0.0426494000
_diffrn_orient_matrix_UB_13      0.0205558000
_diffrn_orient_matrix_UB_21      -0.0880240000
_diffrn_orient_matrix_UB_22      0.0382976000
_diffrn_orient_matrix_UB_23      -0.1425905000
_diffrn_orient_matrix_UB_31      0.0165371000
_diffrn_orient_matrix_UB_32      -0.1258307000
_diffrn_orient_matrix_UB_33      -0.0503819000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0140
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_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       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            26178
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.796
_diffrn_reflns_theta_min         4.381
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.433
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 2190 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         4773
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0193
_refine_ls_R_factor_gt           0.0192
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+0.5140P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0498
_refine_ls_wR_factor_ref         0.0498
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                4759
_reflns_number_total             4773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06115a2.cif
_cod_data_source_block           20201124_sc-13-56a
_cod_database_code               1565338
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.666
_shelx_estimated_absorpt_t_min   0.350
_reflns_odcompleteness_completeness 100.00
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00G(H00G), C00H(H00H)
2.b Aromatic/amide H refined with riding coordinates:
 C007(H007), C00C(H00C), C00D(H00D), C00I(H00I), C00J(H00J), C00M(H00M),
 C00R(H00U), C00S(H00V), C00T(H00W), C00U(H00X)
2.c X=CH2 refined with riding coordinates:
 C006(H00A,H00B), C00Q(H00S,H00T)
2.d Idealised Me refined as rotating group:
 C00N(H00E,H00F,H00K), C00O(H00L,H00N,H00O), C00P(H00P,H00Q,H00R)
;
_shelx_res_checksum              89849
_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 1.714
_oxdiff_exptl_absorpt_empirical_full_min 0.700