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_1566588
_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         'C36 H32 F3 N O5 S'
_chemical_formula_sum            'C36 H32 F3 N O5 S'
_chemical_formula_weight         647.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-01-26
_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                 124.382(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.3277(9)
_cell_length_b                   7.49483(19)
_cell_length_c                   18.2663(6)
_cell_measurement_reflns_used    5890
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.5440
_cell_measurement_theta_min      4.8410
_cell_volume                     3313.6(3)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.999
_diffrn_measured_fraction_theta_max 0.990
_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   -105.00  15.00   0.60    3.00    --  -33.50   0.00 -60.00  200
  2  \w    -93.00 -67.80   0.60    3.00    --  -33.50 -57.00  90.00   42
  3  \w    -49.00  34.40   0.60    3.00    --  -33.50  57.00 -60.00  139
  4  \w     22.00  73.00   0.60    3.00    --   36.47  57.00   0.00   85
  5  \w     76.00 102.40   0.60    3.00    --   36.47  19.00 -30.00   44
  6  \w     79.80 105.00   0.60    3.00    --   36.47  57.00   0.00   42
  7  \w     56.00 106.40   0.60    3.00    --   36.47  37.00  60.00   84
  8  \w     22.00  53.20   0.60    3.00    --   36.47  19.00-150.00   52
  9  \w     19.00  52.00   0.60    3.00    --   36.47  57.00 -60.00   55
 10  \w     19.00  48.40   0.60    3.00    --   36.47  57.00 120.00   49
 11  \w     21.00  47.40   0.60    3.00    --   36.47  37.00  90.00   44
 12  \w     72.00 105.00   0.60    3.00    --   36.47 178.00 -60.00   55
 13  \w     45.00  73.20   0.60    3.00    --   36.47-167.00 -18.00   47
 14  \w      6.00  32.40   0.60    3.00    --   36.47  19.00 -30.00   44
 15  \w     85.00 111.40   0.60    3.00    --   36.47-167.00 -18.00   44
 16  \w     11.00  37.40   0.60    3.00    --   36.47  77.00   0.00   44
 17  \w      9.00  75.00   0.60    3.00    --   36.47  77.00-180.00  110
 18  \w     79.80 105.00   0.60    3.00    --   36.47  57.00 -90.00   42
 19  \w     16.00  67.60   0.60    3.00    --   36.47  77.00  90.00   86
 20  \w     19.00  73.00   0.60    3.00    --   36.47  37.00-120.00   90
 21  \w     42.00  75.00   0.60    3.00    --   36.47  37.00 120.00   55
 22  \w     18.00  47.40   0.60    3.00    --   36.47 -77.00 -60.00   49
 23  \w     76.00 101.20   0.60    3.00    --   36.47  57.00  60.00   42
 24  \w     29.00  62.00   0.60    3.00    --   36.47  57.00 -30.00   55
 25  \w      8.00  42.20   0.60    3.00    --   36.47  77.00 150.00   57
 26  \w     79.00 104.20   0.60   10.00    --  108.00  77.00-180.00   42
 27  \w     82.00 115.60   0.60   10.00    --  108.00  30.00-150.00   56
 28  \w     38.00  88.40   0.60   10.00    --  108.00 -94.00  30.00   84
 29  \w     84.00 113.40   0.60   10.00    --  108.00  30.00 -90.00   49
 30  \w     79.00 104.20   0.60   10.00    --  108.00  77.00 120.00   42
 31  \w    139.00 168.40   0.60   10.00    --  108.00  45.00 120.00   49
 32  \w     39.00 108.00   0.60   10.00    --  108.00 -94.00-180.00  115
 33  \w    121.00 162.40   0.60   10.00    --  108.00  77.00  90.00   69
 34  \w     88.00 119.20   0.60   10.00    --  108.00  45.00 120.00   52
 35  \w    141.00 168.00   0.60   10.00    --  108.00  77.00-150.00   45
 36  \w     88.00 113.20   0.60   10.00    --  108.00  61.00-180.00   42
 37  \w     79.00 104.20   0.60   10.00    --  108.00  77.00  90.00   42
 38  \w     88.00 113.20   0.60   10.00    --  108.00  61.00 150.00   42
 39  \w    129.00 156.00   0.60   10.00    --  108.00  77.00 150.00   45
 40  \w     83.00 108.20   0.60   10.00    --  108.00  30.00 120.00   42
 41  \w    116.80 177.40   0.60   10.00    --  108.00  30.00-120.00  101
 42  \w     79.00 110.20   0.60   10.00    --  108.00  77.00 150.00   52
 43  \w     79.00 104.20   0.60   10.00    --  108.00  77.00-150.00   42
 44  \w    150.00 174.60   0.60   10.00    --  108.00  61.00-120.00   41
 45  \w     83.00 108.20   0.60   10.00    --  108.00  30.00-120.00   42
 46  \w     88.00 114.40   0.60   10.00    --  108.00  45.00-180.00   44
 47  \w     88.00 114.40   0.60   10.00    --  108.00  61.00-120.00   44
 48  \w     63.00 137.40   0.60   10.00    --  108.00  15.00-150.00  124
 49  \w     63.00  89.40   0.60   10.00    --  108.00  15.00 -90.00   44
 50  \w     82.00 117.40   0.60   10.00    --  108.00  30.00 150.00   59
 51  \w     79.00 105.40   0.60   10.00    --  108.00  77.00-120.00   44
 52  \w     83.00 108.20   0.60   10.00    --  108.00  30.00-180.00   42
 53  \w     88.00 114.40   0.60   10.00    --  108.00  61.00 120.00   44
 54  \w     88.00 113.20   0.60   10.00    --  108.00  61.00-150.00   42
 55  \w    120.00 171.00   0.60   10.00    --  108.00  77.00-180.00   85
 56  \w     38.00 128.00   0.60   10.00    --  108.00 -45.00-120.00  150
 57  \w     40.00 127.00   0.60   10.00    --  108.00 -77.00  60.00  145
;
_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      -0.0621462706
_diffrn_orient_matrix_UB_12      -0.0338762361
_diffrn_orient_matrix_UB_13      -0.0445805978
_diffrn_orient_matrix_UB_21      0.0091926044
_diffrn_orient_matrix_UB_22      -0.0033745991
_diffrn_orient_matrix_UB_23      0.0917715124
_diffrn_orient_matrix_UB_31      -0.0102386383
_diffrn_orient_matrix_UB_32      0.2027286219
_diffrn_orient_matrix_UB_33      -0.0059282301
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            15762
_diffrn_reflns_point_group_measured_fraction_full 0.899
_diffrn_reflns_point_group_measured_fraction_max 0.884
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.872
_diffrn_reflns_theta_min         3.652
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.378
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79209
_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    1.298
_exptl_crystal_description       plate
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.280
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1724 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(15)
_refine_ls_extinction_coef       0.00100(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     446
_refine_ls_number_reflns         5649
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0518
_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^)+(0.0877P)^2^+1.0127P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1521
_reflns_Friedel_coverage         0.651
_reflns_Friedel_fraction_full    0.781
_reflns_Friedel_fraction_max     0.758
_reflns_number_gt                5001
_reflns_number_total             5649
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07044d2.cif
_cod_data_source_block           lss2
_cod_original_cell_volume        3313.6(2)
_cod_database_code               1566588
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O5N1S1F3
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.810
_reflns_odcompleteness_completeness 99.94
_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
 F3-S1
 2.2 with sigma of 0.02
 O5A-O4A
 2.5 with sigma of 0.02
 F3A-C22A
 1.35 with sigma of 0.02
 C22A-O5A
 2.5 with sigma of 0.02
 S1A-F3A
 2.5 with sigma of 0.02
 S1A-O5A
 1.5 with sigma of 0.02
 O4A-S1A
 1.5 with sigma of 0.02
 C22-O4A
 1.5 with sigma of 0.02
 C22A-F3A
 1.4 with sigma of 0.02
 F1A-F3A
 2.2 with sigma of 0.02
 F2A-F3A
 2.2 with sigma of 0.02
 C22-S1
 1.65 with sigma of 0.02
 S1-O5
 1.68 with sigma of 0.02
 C22A-S1A
 1.68 with sigma of 0.02
 S1A-O4A
 1.5 with sigma of 0.02
 S1-O4
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1A)
\\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(F3A) \\sim Ueq,
Uanis(F3) \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O5A) \\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S1) = Uanis(S1A)
Uanis(O5) = Uanis(O5A)
Uanis(O4) = Uanis(O4A)
Uanis(O3) = Uanis(O3A)
Uanis(C22) = Uanis(C22A)
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
4. Others
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(C22A)=1-
 FVAR(1)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(C22)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C15(H15)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C30(H30A,H30B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C17(H17), C18(H18),
 C20(H20), C21(H21), C24(H24), C26(H26), C27(H27), C32(H32), C33(H33), C34(H34),
  C35(H35), C36(H36)
5.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C)
;
_shelx_res_checksum              99014
_shelx_hkl_checksum              36769
_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 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.848