Atroposelective Catalytic Asymmetric Allylic Alkylation Reaction for Axially Chiral Anilides with Achiral Morita-Baylis-Hillman Carbonates.
Li, Shou-Lei; Yang, Chen; Wu, Quan; Zheng, Han-Liang; Li, Xin; Cheng, Jin-Pei; Journal of the American Chemical Society 140 (2018) 12836–12843; doi:10.1021/jacs.8b06014

data_4132748
_publ_section_title
;
 Atroposelective Catalytic Asymmetric Allylic Alkylation Reaction for
 Axially Chiral Anilides with Achiral Morita-Baylis-Hillman Carbonates.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12836
_journal_page_last               12843
_journal_paper_doi               10.1021/jacs.8b06014
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C25 H30 I N O3'
_chemical_formula_sum            'C25 H30 I N O3'
_chemical_formula_weight         519.40
_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
_audit_creation_date             2018-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.664(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8222(2)
_cell_length_b                   22.4497(5)
_cell_length_c                   12.2995(3)
_cell_measurement_reflns_used    13559
_cell_measurement_temperature    100.01(13)
_cell_measurement_theta_max      71.2680
_cell_measurement_theta_min      3.5640
_cell_volume                     2435.82(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.979
_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   -102.00 -16.00   1.00    2.00    --  -40.81 -77.00  90.00   86
  2  \w   -110.00 -23.00   1.00    2.00    --  -40.81 -38.00 -30.00   87
  3  \w     49.00  75.00   1.00    2.00    --   40.81-125.00 -60.00   26
  4  \w     74.00 175.00   1.00    3.00    --  100.91  30.00 -90.00  101
  5  \w     48.00 109.00   1.00    3.00    --  100.91 -95.00-120.00   61
  6  \w     46.00 106.00   1.00    3.00    --  100.91 -95.00  60.00   60
  7  \w     42.00 126.00   1.00    3.00    --  100.91 -45.00  90.00   84
  8  \w     77.00 119.00   1.00    3.00    --  100.91 -45.00-120.00   42
  9  \w    -94.00  -4.00   1.00    2.00    --  -41.06 125.00 120.00   90
 10  \w    -31.00  65.00   1.00    2.00    --   41.06 -57.00-120.00   96
 11  \w     92.00 118.00   1.00    3.00    --  100.29 -45.00 -30.00   26
 12  \w     73.00 116.00   1.00    3.00    --  100.29-125.00-180.00   43
 13  \w     18.00  51.00   1.00    3.00    --  100.29 -95.00 -30.00   33
 14  \w     61.00 105.00   1.00    3.00    --  100.29 -95.00 -30.00   44
 15  \w     99.00 139.00   1.00    3.00    --  100.29 125.00-180.00   40
 16  \w     87.00 165.00   1.00    3.00    --  100.29  30.00   0.00   78
 17  \w     35.00  61.00   1.00    3.00    --  100.29 -95.00-180.00   26
 18  \w     67.00  93.00   1.00    3.00    --  100.29 -95.00-180.00   26
 19  \w     39.00  75.00   1.00    3.00    --  100.29 -45.00 -30.00   36
 20  \w     76.00 103.00   1.00    3.00    --  100.29  61.00 120.00   27
 21  \w    118.00 143.00   1.00    3.00    --  100.29  61.00 120.00   25
 22  \w    129.00 155.00   1.00    3.00    --  100.29 125.00  30.00   26
 23  \w     83.00 128.00   1.00    3.00    --  100.29 -61.00-180.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1232353000
_diffrn_orient_matrix_UB_12      0.0180866000
_diffrn_orient_matrix_UB_13      -0.0813708000
_diffrn_orient_matrix_UB_21      -0.1072910000
_diffrn_orient_matrix_UB_22      -0.0161206000
_diffrn_orient_matrix_UB_23      -0.0952361000
_diffrn_orient_matrix_UB_31      -0.0615967000
_diffrn_orient_matrix_UB_32      0.0642058000
_diffrn_orient_matrix_UB_33      -0.0009434000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0634
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            18069
_diffrn_reflns_point_group_measured_fraction_full 0.860
_diffrn_reflns_point_group_measured_fraction_max 0.832
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.445
_diffrn_reflns_theta_min         3.594
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.518
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62918
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.416
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.524
_refine_diff_density_min         -2.001
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Flack x determined using 2775 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     553
_refine_ls_number_reflns         7903
_refine_ls_number_restraints     515
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0485P)^2^+6.2974P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1203
_refine_ls_wR_factor_ref         0.1209
_reflns_Friedel_coverage         0.654
_reflns_Friedel_fraction_full    0.715
_reflns_Friedel_fraction_max     0.677
_reflns_number_gt                7713
_reflns_number_total             7903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06014_si_002.cif
_cod_data_source_block           20180205liujunyan-61h
_cod_database_code               4132748
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.621
_shelx_estimated_absorpt_t_min   0.227
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C43(H43A,H43B)
4.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C35(H35), C28(H28), C37(H37), C9(H9), C36(H36), C5(H5), C6(H6),
 C34(H34), C30(H30), C27(H27), C10(H10), C3(H3), C12(H12), C2(H2), C31(H31)
4.c X=CH2 refined with riding coordinates:
 C45(H45A,H45B), C20(H20A,H20B)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C50(H50A,H50B,H50C), C17(H17A,H17B,
 H17C), C49(H49A,H49B,H49C), C16(H16A,H16B,H16C), C42(H42A,H42B,H42C), C25(H25A,
 H25B,H25C), C40(H40A,H40B,H40C), C48(H48A,H48B,H48C), C23(H23A,H23B,H23C),
 C41(H41A,H41B,H41C)
;
_shelx_res_checksum              80403
_shelx_hkl_checksum              17432
_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 1.676
_oxdiff_exptl_absorpt_empirical_full_min 0.591