Calcium catalyzed enantioselective intramolecular alkene hydroamination with chiral <i>C</i><sub>2</sub>-symmetric bis-amide ligands.
Stegner, Philipp C.; Eyselein, Jonathan; Ballmann, Gerd M.; Langer, Jens; Schmidt, Jochen; Harder, Sjoerd; Dalton transactions (Cambridge, England : 2003) 50 (2021) 3178–3185; doi:10.1039/d1dt00173f

data_7706545
_publ_section_title
;
 Calcium catalyzed enantioselective intramolecular alkene hydroamination
 with chiral <i>C</i><sub>2</sub>-symmetric bis-amide ligands.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3178
_journal_page_last               3185
_journal_paper_doi               10.1039/d1dt00173f
_journal_volume                  50
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C42 H58 Ca N2 O3, C4 H8 O, [+ solvents]'
_chemical_formula_sum            'C46 H66 Ca N2 O4'
_chemical_formula_weight         751.08
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-01-15 deposited with the CCDC.	2021-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5853(5)
_cell_length_b                   19.8516(5)
_cell_length_c                   11.0900(3)
_cell_measurement_reflns_used    13191
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.8970
_cell_measurement_theta_min      3.9790
_cell_volume                     4752.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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   -112.00 -24.00   1.00    7.50    --  -41.69 -57.00 -30.00   88
  2  \w   -114.00 -19.00   1.00    7.50    --  -41.69 -38.00-150.00   95
  3  \w    -59.00  29.00   1.00    7.50    --  -41.69  38.00  30.00   88
  4  \w    -59.00  28.00   1.00    7.50    --  -41.69  38.00 150.00   87
  5  \w     44.00  71.00   1.00    7.50    --   41.69  38.00-180.00   27
  6  \w     90.00 176.00   1.00   30.00    --  106.00  30.00-180.00   86
  7  \w     79.00 106.00   1.00   30.00    --  106.00  77.00 120.00   27
  8  \w     37.00 122.00   1.00   30.00    --  106.00 -45.00 -30.00   85
  9  \w     90.00 176.00   1.00   30.00    --  106.00  61.00   0.00   86
 10  \w     94.00 178.00   1.00   30.00    --  106.00 125.00 -90.00   84
 11  \w     98.00 176.00   1.00   30.00    --  106.00  61.00  60.00   78
 12  \w     25.00 109.00   1.00   30.00    --  106.00 -94.00 -30.00   84
 13  \w    146.00 171.00   1.00   30.00    --  106.00  77.00 120.00   25
 14  \w     82.00 171.00   1.00   30.00    --  106.00  45.00 120.00   89
 15  \w     35.00 117.00   1.00   30.00    --  106.00-125.00 -60.00   82
;
_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      0.0445941000
_diffrn_orient_matrix_UB_12      0.0606000000
_diffrn_orient_matrix_UB_13      0.0030006000
_diffrn_orient_matrix_UB_21      0.0236955000
_diffrn_orient_matrix_UB_22      -0.0225681000
_diffrn_orient_matrix_UB_23      0.1246224000
_diffrn_orient_matrix_UB_31      0.0503778000
_diffrn_orient_matrix_UB_32      -0.0430440000
_diffrn_orient_matrix_UB_33      -0.0611408000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            31954
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.154
_diffrn_reflns_theta_min         3.024
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.434
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.503
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.050
_exptl_crystal_description       block
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.405
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.132
_refine_diff_density_max         1.134
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 3157 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         9461
_refine_ls_number_restraints     2173
_refine_ls_restrained_S_all      0.980
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0751
_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^)+(0.1595P)^2^+1.3655P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2181
_refine_ls_wR_factor_ref         0.2273
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                8401
_reflns_number_total             9461
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00173f2.cif
_cod_data_source_block           hasj160901a
_cod_depositor_comments
'Adding full bibliography for 7706544--7706549.cif.'
_cod_database_code               7706545
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C46H66CaN2O4
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.96
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C27A-C28A \\sim C27A-C30A \\sim C27-C30 \\sim C27A-C29A \\sim C29-C27 \\sim
C27-C28
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 N2A-C26A \\sim N2-C26
 with sigma of 0.02
 C30-C29 \\sim C29-C28 \\sim C30-C28
 with sigma of 0.02
 C36A-C35 \\sim C36-C35 \\sim C37A-C38 \\sim C37-C38 \\sim C40-C39 \\sim
C40A-C39A \\sim C41-C42 ~
 C42A-C41A \\sim C44-C43 \\sim C43A-C44 \\sim C46-C45 \\sim C46A-C45
 with sigma of 0.02
 C41-C40 \\sim C40A-C41A \\sim C44-C45 \\sim C37A-C36A \\sim C36-C37
 with sigma of 0.02
 O3-C39 \\sim O3A-C39A \\sim O3-C42 \\sim O3A-C42A \\sim O4-C43 \\sim O4A-C43A
\\sim O4-C46 \\sim O4A-C46A
 with sigma of 0.02
 C39-C42 \\sim C39A-C42A
 with sigma of 0.02
 C39-C41 \\sim C42-C40 \\sim C39A-C41A \\sim C42A-C40A
 with sigma of 0.02
 Ca1-O3 \\sim Ca1-O3A
 with sigma of 0.02
 N2A-C20A \\sim N2-C20
 with sigma of 0.02
 C12A-C20A \\sim C12-C20 \\sim C9-C1
 with sigma of 0.02
 C10-C1 \\sim C20-C11 \\sim C11A-C20A
 with sigma of 0.02
 C11A-C10 \\sim C2-C1 \\sim C19A-C20A \\sim C20-C19
 with sigma of 0.02
 C30A-C26A \\sim C26A-C29A \\sim C28A-C26A \\sim C30-C26 \\sim C26-C29 \\sim
C28-C26
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim
C19 \\sim C20 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim N2A \\sim
C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A \\sim
C18A \\sim C19A \\sim C20A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim
C30A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within
4A
O3 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim O3A \\sim C39A \\sim C40A
\\sim C41A \\sim C42A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C44 \\sim C45 \\sim O4 \\sim C43 \\sim C46 \\sim O4A \\sim C43A \\sim C46A:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C35 \\sim C38 \\sim C36 \\sim C37 \\sim C36A \\sim C37A: within 4A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 4A
4. Rigid body (RIGU) restrains
 O4, C43, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N2A)=Sof(C11A)=Sof(C12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=
 Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=
 Sof(C28A)=Sof(H28F)=Sof(H28D)=Sof(H28E)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(N2)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=
 Sof(C20)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=FVAR(1)
 Sof(O3A)=Sof(C39A)=Sof(H39D)=Sof(H39C)=Sof(C40A)=Sof(H40D)=Sof(H40C)=
 Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42D)=Sof(H42C)=1-FVAR(2)
 Sof(O3)=Sof(C39)=Sof(H39B)=Sof(H39A)=Sof(C40)=Sof(H40B)=Sof(H40A)=Sof(C41)=
 Sof(H41B)=Sof(H41A)=Sof(C42)=Sof(H42B)=Sof(H42A)=FVAR(2)
 Sof(H44C)=Sof(H44D)=Sof(H45C)=Sof(H45D)=Sof(O4A)=Sof(C43A)=Sof(H43C)=
 Sof(H43D)=Sof(C46A)=Sof(H46D)=Sof(H46C)=1-FVAR(3)
 Sof(H44A)=Sof(H44B)=Sof(H45A)=Sof(H45B)=Sof(O4)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(C46)=Sof(H46B)=Sof(H46A)=FVAR(3)
 Sof(H35C)=Sof(H35D)=Sof(H38C)=Sof(H38D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=
 Sof(C37A)=Sof(H37C)=Sof(H37D)=1-FVAR(4)
 Sof(H35A)=Sof(H35B)=Sof(H38A)=Sof(H38B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=
 Sof(H37A)=Sof(H37B)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C35(H35C,H35D), C38(H38A,H38B), C38(H38C,H38D),
 C44(H44A,H44B), C44(H44C,H44D), C45(H45A,H45B), C45(H45C,H45D), C26(H26A,H26B),
  C36(H36A,H36B), C37(H37A,H37B), C39(H39B,H39A), C40(H40B,H40A), C41(H41B,
 H41A), C42(H42B,H42A), C43(H43A,H43B), C46(H46B,H46A), C26A(H26C,H26D),
 C36A(H36C,H36D), C37A(H37C,H37D), C39A(H39D,H39C), C40A(H40D,H40C), C41A(H41C,
 H41D), C42A(H42D,H42C), C43A(H43C,H43D), C46A(H46D,H46C)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A),
 C18A(H18A), C19A(H19A)
6.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C28A(H28F,H28D,H28E),
 C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23293
_shelx_hkl_checksum              46000
_shelx_fab_checksum              33717
_olex2_date_sample_data_collection 2016-09-01
_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 4.069
_oxdiff_exptl_absorpt_empirical_full_min 0.330