Iridium-catalyzed asymmetric double allylic alkylation of azlactone: efficient access to chiral α-amino acid derivatives
Cheng, Xiang; Shen, Chong; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical Communications  (2022) –; doi:10.1039/D2CC00328G

data_7129723
_publ_section_title
;
 Iridium-catalyzed asymmetric double allylic alkylation of azlactone:
 efficient access to chiral \a-amino acid derivatives
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00328G
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H23 Cl4 N O3'
_chemical_formula_sum            'C28 H23 Cl4 N O3'
_chemical_formula_weight         563.27
_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             2021-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-24 deposited with the CCDC.	2022-02-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.76191(4)
_cell_length_b                   13.60474(5)
_cell_length_c                   16.49635(6)
_cell_measurement_reflns_used    31908
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5900
_cell_measurement_theta_min      4.5940
_cell_volume                     2639.708(16)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_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    -73.00 -29.00   0.50    0.50    --    0.00 -42.00 -17.00   88
  2  \w     93.00 147.00   0.50    0.50    --   94.60  42.00 134.00  108
  3  \w     43.00 102.00   0.50    0.50    --   94.60 -42.00 -17.00  118
  4  \w      5.00  39.00   0.50    0.50    --   94.60 -42.00 -17.00   68
  5  \w    -33.00  31.00   0.50    0.50    --    0.00 -82.00  30.00  128
  6  \w     10.00  56.00   0.50    0.50    --    0.00  19.00 -90.00   92
  7  \w    -45.00  28.00   0.50    0.50    --    0.00 -77.00 -90.00  146
  8  \w      4.00  37.00   0.50    0.50    --    0.00  42.00 134.00   66
  9  \w    -33.00  15.00   0.50    0.50    --    0.00 -82.00 -30.00   96
 10  \w     68.00  94.00   0.50    0.50    --   94.60  69.00-151.52   52
 11  \w      6.00  93.00   0.50    0.50    --   94.60 -30.00-180.00  174
 12  \w    127.00 170.00   0.50    0.50    --   94.60  61.00 -60.00   86
 13  \w     75.00 117.00   0.50    0.50    --   94.60  45.00 -90.00   84
 14  \w    124.00 162.00   0.50    0.50    --   94.60  30.00-180.00   76
 15  \w     71.00  98.00   0.50    0.50    --   94.60  61.00-120.00   54
 16  \w    149.00 175.00   0.50    0.50    --   94.60  61.00-120.00   52
 17  \w     90.00 184.00   0.50    0.50    --   94.60  30.00  90.00  188
 18  \w     77.00 128.00   0.50    0.50    --   94.60  45.00 -60.00  102
 19  \w    108.00 182.00   0.50    0.50    --   94.60  75.00-109.69  148
 20  \w     74.00 110.00   0.50    0.50    --   94.60 -61.00-180.00   72
 21  \w     10.00  38.00   0.50    0.50    --   94.60 -61.00-180.00   56
 22  \w     84.00 110.00   0.50    0.50    --   94.60  30.00-180.00   52
 23  \w    117.00 157.00   0.50    0.50    --   94.60  45.00-150.00   80
 24  \w     80.00 183.00   0.50    0.50    --   94.60  77.00 150.00  206
 25  \w     75.00 108.00   0.50    0.50    --   94.60  45.00-150.00   66
 26  \w     71.00  96.00   0.50    0.50    --   94.60  61.00-150.00   50
 27  \w     35.00 124.00   0.50    0.50    --   94.60 -77.00  90.00  178
 28  \w     73.00  99.00   0.50    0.50    --   94.60  54.00-121.89   52
 29  \w    159.00 184.00   0.50    0.50    --   94.60  69.00-151.52   50
 30  \w     73.00 110.00   0.50    0.50    --   94.60  55.00 -89.61   74
 31  \w     80.00 131.00   0.50    0.50    --   94.60  77.00  30.00  102
 32  \w     79.00 160.00   0.50    0.50    --   94.60  30.00-120.00  162
 33  \w     66.00  91.00   0.50    0.50    --   94.60  75.00-109.69   50
 34  \w     71.00  96.00   0.50    0.50    --   94.60  61.00-180.00   50
 35  \w      7.00 106.00   0.50    0.50    --   94.60 -45.00-180.00  198
;
_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      0.0528201000
_diffrn_orient_matrix_UB_12      -0.0315817000
_diffrn_orient_matrix_UB_13      -0.0813311000
_diffrn_orient_matrix_UB_21      -0.1119930000
_diffrn_orient_matrix_UB_22      -0.0513276000
_diffrn_orient_matrix_UB_23      -0.0235150000
_diffrn_orient_matrix_UB_31      -0.0425563000
_diffrn_orient_matrix_UB_32      0.0959039000
_diffrn_orient_matrix_UB_33      -0.0394351000
_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  0.0239
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            35174
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.996
_diffrn_reflns_theta_min         4.212
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.330
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63291
_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    1.417
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 2282 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(2)
_refine_ls_extinction_coef       0.00078(9)
_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   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         5307
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0193
_refine_ls_R_factor_gt           0.0193
_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^+0.7437P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0514
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                5297
_reflns_number_total             5307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00328g2.cif
_cod_data_source_block           20210713_cgxg-2-152
_cod_original_cell_volume        2639.710(17)
_cod_database_code               7129723
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.671
_shelx_estimated_absorpt_t_min   0.411
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00E(H00E), C00L(H00L)
2.b Aromatic/amide H refined with riding coordinates:
 N008(H008), C00B(H00B), C00C(H00C), C00G(H00G), C00H(H00H), C00J(H00J),
 C00O(H00O), C00P(H00P), C00R(H00R), C00T(H00T), C00V(H00V), C00X(H00X),
 C00Y(H00Y), C010(H010)
2.c X=CH2 refined with riding coordinates:
 C00M(H00A,H00D), C00W(H00F,H00I)
2.d Idealised Me refined as rotating group:
 C00Z(H00K,H00M,H00N)
;
_shelx_res_checksum              60133
_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 1.929
_oxdiff_exptl_absorpt_empirical_full_min 0.764