Asymmetric [3 + 2] photocycloadditions of cyclopropylamines with electron-rich and electron-neutral olefins
Dai, Yating; Liang, Shuangshuang; Zeng, Guangkuo; Huang, Hongchun; Zhao, Xiaowei; Cao, Shanshan; Jiang, Zhiyong; Chemical Science  (2022) –; doi:10.1039/D1SC07044D

data_1566589
_publ_section_title
;
 Asymmetric [3 + 2] photocycloadditions of cyclopropylamines with
 electron-rich and electron-neutral olefins
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC07044D
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H34 Cl N O2'
_chemical_formula_sum            'C33 H34 Cl N O2'
_chemical_formula_weight         512.06
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2021-04-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-04-27 deposited with the CCDC.	2022-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.526(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.1324(7)
_cell_length_b                   7.5493(6)
_cell_length_c                   16.7445(13)
_cell_measurement_reflns_used    3626
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.3700
_cell_measurement_theta_min      3.9500
_cell_volume                     1407.18(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.962
_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      2.00  32.00   1.00    2.00    --  -33.50  57.00  90.00   30
  2  \w    -65.00 -15.00   1.00    2.00    --  -33.50 -57.00 150.00   50
  3  \w   -108.00 -80.00   1.00    2.00    --  -33.50 178.00  90.00   28
  4  \w     17.00  43.00   1.00    2.00    --   36.47  19.00 -30.00   26
  5  \w     -3.00  75.00   1.00    2.00    --   36.47 -99.00  90.00   78
  6  \w     68.00 106.00   1.00    2.00    --   36.47  37.00-150.00   38
  7  \w     20.00 104.00   1.00    2.00    --   36.47  57.00 -90.00   84
  8  \w     25.00  50.00   1.00    2.00    --   36.47  77.00  30.00   25
  9  \w    -31.00  53.00   1.00    2.00    --   36.47 -57.00-180.00   84
 10  \w     38.00  64.00   1.00    2.00    --   36.47  19.00   0.00   26
 11  \w     -8.00  19.00   1.00    2.00    --   36.47 106.00 109.10   27
 12  \w     15.00  73.00   1.00    2.00    --   36.47  77.00 -60.00   58
 13  \w      9.00  63.00   1.00    2.00    --   36.47  77.00-180.00   54
 14  \w     83.00 109.00   1.00    2.00    --   36.47  19.00-120.00   26
 15  \w     55.00  80.00   1.00    2.00    --   36.47  19.00 -30.00   25
 16  \w     76.00 106.00   1.00    2.00    --   36.47 178.00  30.00   30
 17  \w     58.00 108.00   1.00    2.00    --   36.47 178.00-120.00   50
 18  \w     15.00  48.00   1.00    2.00    --   36.47  37.00-150.00   33
 19  \w    130.00 177.00   1.00    9.00    --  108.00  77.00 -30.00   47
 20  \w     37.00  77.00   1.00    9.00    --  108.00 -30.00-150.00   40
 21  \w     79.00 105.00   1.00    9.00    --  108.00  77.00 -30.00   26
 22  \w     39.00 108.00   1.00    9.00    --  108.00 -94.00 -30.00   69
 23  \w     82.00 114.00   1.00    9.00    --  108.00  30.00   0.00   32
 24  \w    139.00 175.00   1.00    9.00    --  108.00  61.00-150.00   36
 25  \w     82.00 112.00   1.00    9.00    --  108.00  30.00 -60.00   30
 26  \w     88.00 114.00   1.00    9.00    --  108.00  61.00 -60.00   26
 27  \w     57.00 128.00   1.00    9.00    --  108.00 -61.00 -60.00   71
 28  \w     90.00 125.00   1.00    9.00    --  108.00 -30.00-150.00   35
 29  \w     84.00 135.00   1.00    9.00    --  108.00  30.00-120.00   51
 30  \w     80.00 112.00   1.00    9.00    --  108.00-111.00 120.00   32
 31  \w     79.00 105.00   1.00    9.00    --  108.00  77.00-150.00   26
 32  \w     84.00 109.00   1.00    9.00    --  108.00 -94.00-120.00   25
 33  \w     89.00 116.00   1.00    9.00    --  108.00  61.00-150.00   27
 34  \w     79.00 105.00   1.00    9.00    --  108.00  77.00-120.00   26
 35  \w    124.00 170.00   1.00    9.00    --  108.00  77.00 -60.00   46
 36  \w    133.00 165.00   1.00    9.00    --  108.00  30.00 -90.00   32
 37  \w     98.00 178.00   1.00    9.00    --  108.00  45.00   0.00   80
 38  \w     89.00 116.00   1.00    9.00    --  108.00  61.00-120.00   27
 39  \w     38.00  71.00   1.00    9.00    --  108.00 -94.00 120.00   33
 40  \w     79.00 105.00   1.00    9.00    --  108.00  77.00 -60.00   26
 41  \w     88.00 117.00   1.00    9.00    --  108.00  61.00 -30.00   29
 42  \w     88.00 138.00   1.00    9.00    --  108.00  61.00 -90.00   50
 43  \w    109.00 176.00   1.00    9.00    --  108.00  77.00 -90.00   67
 44  \w     83.00 108.00   1.00    9.00    --  108.00  30.00 -30.00   25
 45  \w     89.00 114.00   1.00    9.00    --  108.00  45.00-120.00   25
 46  \w     94.00 120.00   1.00    9.00    --  108.00  45.00 -60.00   26
 47  \w     79.00 105.00   1.00    9.00    --  108.00  77.00 -90.00   26
 48  \w     85.00 112.00   1.00    9.00    --  108.00  30.00 -90.00   27
 49  \w     37.00  75.00   1.00    9.00    --  108.00-111.00 120.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1297477000
_diffrn_orient_matrix_UB_12      -0.0334456000
_diffrn_orient_matrix_UB_13      0.0288312000
_diffrn_orient_matrix_UB_21      -0.0321286000
_diffrn_orient_matrix_UB_22      0.0726778000
_diffrn_orient_matrix_UB_23      0.0831125000
_diffrn_orient_matrix_UB_31      -0.0355450000
_diffrn_orient_matrix_UB_32      -0.1877345000
_diffrn_orient_matrix_UB_33      0.0271264000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12005
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.554
_diffrn_reflns_theta_min         3.971
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.423
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40388
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.123
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1304 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.018(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     350
_refine_ls_number_reflns         4982
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0717P)^2^+0.0634P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1279
_refine_ls_wR_factor_ref         0.1415
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    0.861
_reflns_Friedel_fraction_max     0.807
_reflns_number_gt                4027
_reflns_number_total             4982
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07044d2.cif
_cod_data_source_block           20210476
_cod_database_code               1566589
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O5N2
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.837
_reflns_odcompleteness_completeness 99.89
_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
 C15-C14
 1.53 with sigma of 0.02
 C14A-C15A
 1.53 with sigma of 0.02
 C16A-C15A
 1.53 with sigma of 0.02
 C13-C14
 1.53 with sigma of 0.02
 C13-C14A
 1.53 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C14) = Uanis(C14A)
Uanis(C16) = Uanis(C16A)
Uanis(C15) = Uanis(C15A)
4. Others
 Sof(H13A)=Sof(H17A)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=
 Sof(H15D)=Sof(C16A)=Sof(H16C)=Sof(H16D)=1-FVAR(1)
 Sof(H13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H17)=FVAR(1)
5.a Riding coordinates:
 C31(H31A,H31B,H31C)
5.b Ternary CH refined with riding coordinates:
 C13(H13), C13(H13A), C17(H17), C17(H17A)
5.c Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C24(H24A,H24B), C14A(H14C,
 H14D), C15A(H15C,H15D), C16A(H16C,H16D)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C19(H19),
 C21(H21), C22(H22), C27(H27), C28(H28), C29(H29)
5.e Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_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 2.328
_oxdiff_exptl_absorpt_empirical_full_min 0.755