Isothiourea-catalysed enantioselective Michael addition of N-heterocyclic pronucleophiles to α,β-unsaturated aryl esters
Shu, Chang; Liu, Honglei; Slawin, Alexandra M. Z.; Carpenter-Warren, Cameron; Smith, Andrew D.; Chemical Science 11 (2020) 241–247; doi:10.1039/C9SC04303A

data_1552458
_publ_section_title
;
 Isothiourea-catalysed enantioselective Michael addition of N-heterocyclic
 pronucleophiles to \a,\b-unsaturated aryl esters
;
_journal_issue                   1
_journal_name_full               'Chemical Science'
_journal_page_first              241
_journal_page_last               247
_journal_paper_doi               10.1039/C9SC04303A
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H26 F3 N3 O2'
_chemical_formula_sum            'C28 H26 F3 N3 O2'
_chemical_formula_weight         493.52
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_update_record
;
2019-07-05 deposited with the CCDC.    2019-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.584(2)
_cell_angle_gamma                90
_cell_formula_units_Z            10
_cell_length_a                   13.5575(2)
_cell_length_b                   23.9425(3)
_cell_length_c                   19.8418(3)
_cell_measurement_reflns_used    27009
_cell_measurement_temperature    173
_cell_measurement_theta_max      67.5260
_cell_measurement_theta_min      2.2120
_cell_volume                     6428.06(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_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_temperature      173
_diffrn_detector                 'PILATUS P100'
_diffrn_measured_fraction_theta_full 0.9976
_diffrn_measured_fraction_theta_max 0.9852
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f      0.00 200.00   0.50   30.00   0.00 -30.00   0.00    --   400
  2  \w    -72.00   1.00   0.50   30.00    --  -30.00 -72.00 -90.00  146
  3  \w   -113.00 -71.00   0.50   30.00    --  -30.00 180.00 -45.00   84
  4  \f      0.00 200.00   0.50   30.00   0.00 -67.00   0.00    --   400
  5  \w    -85.00 -13.00   0.50   30.00    --  -67.00  72.00  90.00  144
  6  \w   -133.00 -93.00   0.50   30.00    --  -67.00 180.00   0.00   80
  7  \w    -85.00 -12.00   0.50   30.00    --  -67.00  72.00 -90.00  146
  8  \w   -126.00 -86.00   0.50   30.00    --  -67.00 180.00-180.00   80
  9  \f      0.00 200.00   0.50   30.00 -25.00-110.00   0.00    --   400
 10  \w   -128.00 -20.00   0.50   30.00    -- -110.00  72.00-135.00  216
 11  \w   -128.00 -20.00   0.50   30.00    -- -110.00  72.00  45.00  216
 12  \w   -115.00 -20.00   0.50   30.00    -- -110.00  72.00 -45.00  190
 13  \w   -113.00 -23.00   0.50   30.00    -- -110.00  72.00 135.00  180
 14  \w   -141.00 -46.00   0.50   30.00    -- -110.00 180.00 -90.00  190
 15  \w   -141.00 -46.00   0.50   30.00    -- -110.00 180.00-180.00  190
 16  \w   -141.00 -59.00   0.50   30.00    -- -110.00 180.00  90.00  164
 17  \w   -141.00 -55.00   0.50   30.00    -- -110.00 180.00   0.00  172
 18  \w   -141.00 -59.00   0.50   30.00    -- -110.00 180.00  45.00  164
 19  \w   -141.00 -78.00   0.50   30.00    -- -110.00 180.00 -45.00  126
 20  \w   -140.00 -77.00   0.50   30.00    -- -110.00 180.00-135.00  126
 21  \w   -140.00 -56.00   0.50   30.00    -- -110.00 180.00 135.00  168
 22  \w    -91.00 -90.50   0.50   30.00    --  -30.00  45.00   0.00    1
;
_diffrn_measurement_device       'Rigaku XTALAB P100'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0771980000
_diffrn_orient_matrix_UB_12      -0.0471000000
_diffrn_orient_matrix_UB_13      0.0081888000
_diffrn_orient_matrix_UB_21      0.0539858000
_diffrn_orient_matrix_UB_22      0.0238755000
_diffrn_orient_matrix_UB_23      -0.0596387000
_diffrn_orient_matrix_UB_31      0.0639151000
_diffrn_orient_matrix_UB_32      0.0367782000
_diffrn_orient_matrix_UB_33      0.0492879000
_diffrn_radiation_monochromator  'confocal optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0600
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            68106
_diffrn_reflns_point_group_measured_fraction_full 0.947
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.615
_diffrn_reflns_theta_min         2.231
_diffrn_source                   'rotating anode'
_exptl_absorpt_coefficient_mu    0.802
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58005
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2580
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 7515 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_coef       0.00134(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   0.998
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1647
_refine_ls_number_reflns         22181
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0722P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1046
_refine_ls_wR_factor_ref         0.1093
_reflns_Friedel_coverage         0.849
_reflns_Friedel_fraction_full    0.896
_reflns_Friedel_fraction_max     0.881
_reflns_number_gt                18519
_reflns_number_total             22181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04303a2.cif
_cod_data_source_block           29major
_cod_depositor_comments
;Adding full bibliography for 1552456--1552458.cif.

 Adding full bibliography for 1552456--1552458.cif.
;
_cod_database_code               1552458
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.76
_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. Restrained distances
 N1-H1 = N31-H31 = N61-H61 = N91-H91 = N121-H121
 0.98 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C1(H1A), C31(H31A), C61(H61A), C91(H91A), C121(H12A)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C22(H22A,H22B), C32(H32A,H32B), C34(H34A,H34B),
 C52(H52A,H52B), C62(H62A,H62B), C64(H64A,H64B), C82(H82A,H82B), C92(H92A,H92B),
  C94(H94A,H94B), C112(H11D,H11E), C122(H12B,H12C), C124(H12D,H12E), C142(H14D,
 H14E)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C36(H36),
  C37(H37), C38(H38), C39(H39), C40(H40), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C66(H66),
  C67(H67), C68(H68), C69(H69), C70(H70), C76(H76), C77(H77), C78(H78),
 C79(H79), C80(H80), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C96(H96),
  C97(H97), C98(H98), C99(H99), C100(H100), C106(H106), C107(H107), C108(H108),
 C109(H109), C110(H110), C114(H114), C115(H115), C116(H116), C117(H117),
 C118(H118), C126(H126), C127(H127), C128(H128), C129(H129), C130(H130),
 C136(H136), C137(H137), C138(H138), C139(H139), C140(H140), C144(H144),
 C145(H145), C146(H146), C147(H147), C148(H148)
3.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C51(H51A,H51B,H51C), C81(H81A,H81B,H81C), C111(H11A,H11B,
 H11C), C141(H14A,H14B,H14C)
;
_shelx_res_checksum              61270
_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 2.363
_oxdiff_exptl_absorpt_empirical_full_min 0.432