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_7706548
_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         'C46 H43.516 Ca N4 O2, C4 H10 O'
_chemical_formula_sum            'C50 H53.52 Ca N4 O3'
_chemical_formula_weight         798.57
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                   11.26267(11)
_cell_length_b                   11.38212(12)
_cell_length_c                   32.9097(3)
_cell_measurement_reflns_used    19690
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      73.5110
_cell_measurement_theta_min      4.0620
_cell_volume                     4218.80(7)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -82.00  39.00   1.00    5.00    --  -40.90  19.00-150.00  121
  2  \w    -65.00  33.00   1.00    5.00    --  -40.90  38.00  30.00   98
  3  \w     16.00 115.00   1.00    5.00    --   40.90  38.00 120.00   99
  4  \w     23.00  97.00   1.00    5.00    --   40.90-125.00-180.00   74
  5  \w     23.00  97.00   1.00    5.00    --   40.90-125.00 -60.00   74
  6  \w     34.00 132.00   1.00   20.00    --  106.54 -45.00 -60.00   98
  7  \w     24.00 109.00   1.00   20.00    --  106.54 -94.00 -30.00   85
  8  \w     30.00 139.00   1.00   20.00    --  106.54 -77.00  60.00  109
  9  \w     33.00 122.00   1.00   20.00    --  106.54-125.00 -90.00   89
 10  \w     81.00 178.00   1.00   20.00    --  106.54  45.00   0.00   97
 11  \w     81.00 178.00   1.00   20.00    --  106.54  45.00  30.00   97
 12  \w     81.00 178.00   1.00   20.00    --  106.54  45.00 150.00   97
 13  \w     78.00 178.00   1.00   20.00    --  106.54  30.00  90.00  100
 14  \w     94.00 178.00   1.00   20.00    --  106.54 125.00  30.00   84
 15  \w   -114.00 -13.00   1.00    5.00    --  -40.90 -57.00-120.00  101
 16  \w   -117.00 -42.00   1.00    5.00    --  -40.90 -77.00  60.00   75
 17  \w      8.00 117.00   1.00    5.00    --   40.90  77.00-180.00  109
 18  \w      8.00 117.00   1.00    5.00    --   40.90  77.00   0.00  109
;
_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      -0.0184354000
_diffrn_orient_matrix_UB_12      -0.1334668000
_diffrn_orient_matrix_UB_13      0.0044537000
_diffrn_orient_matrix_UB_21      0.0498069000
_diffrn_orient_matrix_UB_22      0.0055032000
_diffrn_orient_matrix_UB_23      0.0435685000
_diffrn_orient_matrix_UB_31      -0.1260422000
_diffrn_orient_matrix_UB_32      0.0216629000
_diffrn_orient_matrix_UB_33      0.0165653000
_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  0.0341
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            40928
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.617
_diffrn_reflns_theta_min         4.110
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.653
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.483
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       needle
_exptl_crystal_F_000             1702
_exptl_crystal_size_max          0.341
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 3278 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     575
_refine_ls_number_reflns         8387
_refine_ls_number_restraints     270
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0258P)^2^+1.9598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0792
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                8048
_reflns_number_total             8387
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00173f2.cif
_cod_data_source_block           hasj171016a
_cod_depositor_comments
'Adding full bibliography for 7706544--7706549.cif.'
_cod_original_cell_volume        4218.79(7)
_cod_database_code               7706548
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C50H53.5CaN4O3
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.603
_reflns_odcompleteness_completeness 99.95
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O4 \\sim O2 \\sim C51 \\sim C45 \\sim C54 \\sim C46 \\sim C53 \\sim C52 \\sim
C44 \\sim C43: within 4A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 4A
3. Others
 Sof(C53)=Sof(H53a)=Sof(H53b)=Sof(C52)=Sof(H52a)=Sof(H52b)=Sof(O4)=Sof(C54)=
 Sof(H54a)=Sof(H54b)=Sof(C51)=Sof(H51a)=Sof(H51b)=1-FVAR(1)
 Sof(O2)=Sof(C43)=Sof(H43a)=Sof(H43b)=Sof(C45)=Sof(H45a)=Sof(H45b)=Sof(C44)=
 Sof(H44a)=Sof(H44b)=Sof(H44c)=Sof(C46)=Sof(H46a)=Sof(H46b)=Sof(H46c)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C41(H41a,H41b), C47(H47a,H47b), C49(H49a,H49b), C39(H39a,H39b), C43(H43a,
 H43b), C45(H45a,H45b), C53(H53a,H53b), C52(H52a,H52b), C54(H54a,H54b),
 C51(H51a,H51b)
4.b Aromatic/amide H refined with riding coordinates:
 C36(H36), C3(H3), C13(H13), C38(H38), C16(H16), C2(H2), C37(H37), C19(H19),
 C18(H18), C31(H31), C29(H29), C22(H22), C33(H33), C15(H15), C27(H27), C28(H28),
  C23(H23), C7(H7), C32(H32), C14(H14), C8(H8), C5(H5), C24(H24), C6(H6)
4.c Idealised Me refined as rotating group:
 C50(H50a,H50b,H50c), C48(H48a,H48b,H48c), C42(H42a,H42b,H42c), C40(H40a,H40b,
 H40c), C44(H44a,H44b,H44c), C46(H46a,H46b,H46c)
;
_shelx_res_checksum              95933
_shelx_hkl_checksum              53891
_olex2_date_sample_data_collection 2017-10-16
_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 1.248
_oxdiff_exptl_absorpt_empirical_full_min 0.812