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_1565340
_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         'C21 H14 Cl4 I N O2'
_chemical_formula_sum            'C21 H14 Cl4 I N O2'
_chemical_formula_weight         581.03
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-07-14 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                87.954(3)
_cell_angle_beta                 80.589(3)
_cell_angle_gamma                89.897(3)
_cell_formula_units_Z            2
_cell_length_a                   8.2099(3)
_cell_length_b                   11.6051(4)
_cell_length_c                   12.1577(5)
_cell_measurement_reflns_used    15814
_cell_measurement_temperature    296.64(19)
_cell_measurement_theta_max      71.0010
_cell_measurement_theta_min      3.6270
_cell_volume                     1142.02(7)
_computing_cell_refinement
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_computing_data_collection
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_computing_data_reduction
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.64(19)
_diffrn_detector                 'Hybrid Pixel Counting (HPC) detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HyPix-6000HE'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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    -33.00  94.00   0.50    0.50    --    5.00  76.00 150.00  254
  2  \w    -84.00  42.00   0.50    0.50    --    5.00 -37.00  30.00  252
  3  \w    -32.00  94.00   0.50    0.50    --    5.00  37.00 -30.00  252
  4  \w   -136.00  -8.00   0.50    0.50    --  -46.70 -76.00 -30.00  256
  5  \w   -136.00  -8.00   0.50    0.50    --  -46.70 -76.00-150.00  256
  6  \w   -136.00  -8.00   0.50    0.50    --  -46.70 -76.00 -90.00  256
  7  \w   -136.00  -8.00   0.50    0.50    --  -46.70 -76.00  60.00  256
  8  \w   -136.00 -13.00   0.50    0.50    --  -46.70 -57.00  90.00  246
  9  \w    -80.00  43.00   0.50    0.50    --  -46.70  57.00-120.00  246
 10  \w   -187.00 -61.00   0.50    0.50    --  -97.30 -69.00 112.65  252
 11  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00  74.62  256
 12  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -74.00 148.90  256
 13  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -75.00 -53.72  256
 14  \w   -187.00 -60.00   0.50    0.50    --  -97.30 -72.00-147.21  254
 15  \w   -187.00 -60.00   0.50    0.50    --  -97.30 -73.00-111.00  254
 16  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -74.00 160.03  256
 17  \w   -136.00  -8.00   0.50    0.50    --  -97.30  76.00-120.00  256
 18  \w   -136.00  -8.00   0.50    0.50    --  -97.30  76.00-180.00  256
 19  \w   -136.00  -8.00   0.50    0.50    --  -97.30  76.00 -30.00  256
 20  \w   -136.00  -8.00   0.50    0.50    --  -97.30  76.00  30.00  256
 21  \w   -187.00 -60.00   0.50    0.50    --  -97.30 -73.00   8.34  254
 22  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00-180.00  256
 23  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00  51.47  256
 24  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00 -60.00  256
 25  \w   -187.00 -62.00   0.50    0.50    --  -97.30 -68.00 -92.67  250
 26  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00-120.00  256
 27  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -75.00  33.69  256
 28  \w   -187.00 -62.00   0.50    0.50    --  -97.30 -68.00  95.03  250
 29  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00 -90.00  256
 30  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00  90.00  256
 31  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00 -15.15  256
 32  \w   -187.00 -63.00   0.50    0.50    --  -97.30 -62.00 176.58  248
 33  \w   -136.00  -8.00   0.50    0.50    --  -97.30  76.00  90.00  256
 34  \w   -187.00 -59.00   0.50    0.50    --  -97.30 -76.00 -35.12  256
 35  \w   -136.00  -8.00   0.50    0.50    --  -46.70 -76.00-180.00  256
 36  \w   -136.00  43.00   0.50    0.50    --  -46.70   0.00-180.00  358
 37  \w   -136.00  43.00   0.50    0.50    --  -46.70   0.00-150.00  358
 38  \w   -136.00   3.00   0.50    0.50    --  -46.70   0.00-120.00  278
 39  \w   -136.00 -13.00   0.50    0.50    --  -46.70 -57.00 -60.00  246
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       'profile data from \w-scans and \phi-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0201039000
_diffrn_orient_matrix_UB_12      -0.1281241000
_diffrn_orient_matrix_UB_13      -0.0242738000
_diffrn_orient_matrix_UB_21      -0.0381454000
_diffrn_orient_matrix_UB_22      -0.0292280000
_diffrn_orient_matrix_UB_23      0.1262016000
_diffrn_orient_matrix_UB_31      -0.1852568000
_diffrn_orient_matrix_UB_32      0.0193635000
_diffrn_orient_matrix_UB_33      -0.0017680000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'VariMax VHF'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1302
_diffrn_reflns_av_unetI/netI     0.0556
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35246
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        64.983
_diffrn_reflns_theta_max         64.983
_diffrn_reflns_theta_min         3.688
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku MicroMax-007HF'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    15.471
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34370
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.690
_exptl_crystal_description       plate
_exptl_crystal_F_000             568
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.982
_refine_diff_density_min         -0.723
_refine_diff_density_rms         0.150
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.001(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         7558
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0738
_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^)+(0.1592P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2029
_refine_ls_wR_factor_ref         0.2072
_reflns_Friedel_coverage         0.958
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                6921
_reflns_number_total             7558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06115a2.cif
_cod_data_source_block           wcj-cx-15-72-20210223-rt
_cod_database_code               1565340
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.747
_shelx_estimated_absorpt_t_min   0.577
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     39.93
_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:
 C33(H33), C13(H13), C32(H32), C28(H28), C7(H7), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C4(H4), C27(H27), C42(H42), C38(H38), C40(H40), C8(H8),
 C21(H21), C29(H29), C17(H17), C25(H25), C19(H19), C23(H23)
2.d X=CH2 refined with riding coordinates:
 C9(H9A,H9B), C30(H30A,H30B)
;
_shelx_res_checksum              5873
_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 2.937
_oxdiff_exptl_absorpt_empirical_full_min 0.345