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_1565339
_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         'C29 H28 Br N O2'
_chemical_formula_sum            'C29 H28 Br N O2'
_chemical_formula_weight         502.43
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-07-14 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.53030(10)
_cell_length_b                   8.69550(10)
_cell_length_c                   39.2876(3)
_cell_measurement_reflns_used    15907
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.5460
_cell_measurement_theta_min      4.5010
_cell_volume                     2572.54(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.986
_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    -70.00 -11.00   0.50    0.50    --    0.00 -19.00-180.00  118
  2  \w    -22.00  21.00   0.50    0.50    --    0.00  57.00-150.00   86
  3  \w     29.00  60.00   0.50    0.50    --    0.00  57.00-150.00   62
  4  \w    -33.00  30.00   0.50    0.50    --    0.00 -82.00  30.00  126
  5  \w    -33.00  31.00   0.50    0.50    --    0.00 -82.00 120.00  128
  6  \w     -3.00  28.00   0.50    0.50    --    0.00 -77.00-120.00   62
  7  \w     56.00 116.00   0.50    0.50    --   94.60 -82.00  90.00  120
  8  \w    136.00 183.00   0.50    0.50    --   94.60  30.00 -60.00   94
  9  \w      5.00 118.00   0.50    0.50    --   94.60 -61.00  90.00  226
 10  \w     92.00 127.00   0.50    0.50    --   94.60  30.00 -60.00   70
 11  \w     40.00 116.00   0.50    0.50    --   94.60 -82.00-120.00  152
 12  \w     81.00 184.00   0.50    0.50    --   94.60  77.00-150.00  206
 13  \w     33.00  79.00   0.50    0.50    --   94.60 -82.00 -90.00   92
 14  \w     19.00 116.00   0.50    0.50    --   94.60 -15.00-180.00  194
 15  \w     71.00 142.00   0.50    0.50    --   94.60  61.00-120.00  142
 16  \w     85.00 110.00   0.50    0.50    --   94.60 -45.00  30.00   50
 17  \w      6.00  49.00   0.50    0.50    --   94.60 -45.00  30.00   86
 18  \w     76.00 182.00   0.50    0.50    --   94.60  15.00   0.00  212
 19  \w     71.00 157.00   0.50    0.50    --   94.60  15.00  90.00  172
 20  \w     94.00 120.00   0.50    0.50    --   94.60  82.00-180.00   52
 21  \w     98.00 124.00   0.50    0.50    --   94.60  82.00 -90.00   52
 22  \w     15.00  91.00   0.50    0.50    --   94.60 -30.00 150.00  152
;
_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      -0.0668474000
_diffrn_orient_matrix_UB_12      0.1120738000
_diffrn_orient_matrix_UB_13      -0.0275460000
_diffrn_orient_matrix_UB_21      -0.0631331000
_diffrn_orient_matrix_UB_22      0.1117904000
_diffrn_orient_matrix_UB_23      0.0279044000
_diffrn_orient_matrix_UB_31      0.1827430000
_diffrn_orient_matrix_UB_32      0.0795849000
_diffrn_orient_matrix_UB_33      -0.0004335000
_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  0.0390
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            26604
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.997
_diffrn_reflns_theta_min         4.502
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.364
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80504
_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    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.257
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 2035 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.026(6)
_refine_ls_extinction_coef       0.00046(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         5128
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0279
_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^)+(0.0350P)^2^+0.8187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0727
_refine_ls_wR_factor_ref         0.0731
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                5020
_reflns_number_total             5128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06115a2.cif
_cod_data_source_block           20210115_sc-14-148a
_cod_database_code               1565339
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.649
_reflns_odcompleteness_completeness 99.93
_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:
 C007(H007), C00D(H00D)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00B(H00B), C00C(H00C), C00E(H00E), C00F(H00F), C00G(H00G),
 C00P(H00P), C00Q(H00Q), C00S(H00S), C00U(H00W), C00V(H00X), C00W(H00Y),
 C00X(H00Z)
2.c X=CH2 refined with riding coordinates:
 C00M(H00M,H00N), C00R(H00O,H00R)
2.d Idealised Me refined as rotating group:
 C00K(H00A,H00H,H00I), C00L(H00J,H00K,H00L), C00T(H00T,H00U,H00V)
;
_shelx_res_checksum              56114
_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 1.934
_oxdiff_exptl_absorpt_empirical_full_min 0.695