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_7706547
_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         'C62 H62 Ca N2 O3, 4(C4 H8 O)'
_chemical_formula_sum            'C78 H94 Ca N2 O7'
_chemical_formula_weight         1211.63
_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                   11.46322(13)
_cell_length_b                   18.50990(18)
_cell_length_c                   31.3065(3)
_cell_measurement_reflns_used    24295
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.2890
_cell_measurement_theta_min      3.6830
_cell_volume                     6642.71(12)
_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(2)
_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    -96.00 -26.00   1.00    3.00    --  -41.69 125.00-150.00   70
  2  \w   -106.00 -26.00   1.00    3.00    --  -41.69 -38.00 -90.00   80
  3  \w   -105.00 -66.00   1.00    3.00    --  -41.69 -38.00   0.00   39
  4  \w   -114.00 -19.00   1.00    3.00    --  -41.69 -38.00  90.00   95
  5  \w   -104.00 -19.00   1.00    3.00    --  -41.69 -38.00-180.00   85
  6  \w     55.00 121.00   1.00   12.00    --  106.00-125.00 -60.00   66
  7  \w     39.00 126.00   1.00   12.00    --  106.00 -30.00-180.00   87
  8  \w     46.00 137.00   1.00   12.00    --  106.00 -77.00 -90.00   91
  9  \w     41.00 134.00   1.00   12.00    --  106.00 -61.00  90.00   93
 10  \w     53.00 121.00   1.00   12.00    --  106.00-125.00 120.00   68
 11  \w     34.00 128.00   1.00   12.00    --  106.00 -30.00   0.00   94
 12  \w     36.00 122.00   1.00   12.00    --  106.00 -30.00 -90.00   86
 13  \w     29.00 150.00   1.00   12.00    --  106.00 -15.00  90.00  121
;
_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      0.0766334000
_diffrn_orient_matrix_UB_12      -0.0217617000
_diffrn_orient_matrix_UB_13      0.0383446000
_diffrn_orient_matrix_UB_21      -0.0310648000
_diffrn_orient_matrix_UB_22      -0.0799672000
_diffrn_orient_matrix_UB_23      -0.0075666000
_diffrn_orient_matrix_UB_31      0.1059113000
_diffrn_orient_matrix_UB_32      -0.0076437000
_diffrn_orient_matrix_UB_33      -0.0299155000
_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  0.0329
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            44568
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.489
_diffrn_reflns_theta_min         4.107
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.255
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.601
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.212
_exptl_crystal_description       plank
_exptl_crystal_F_000             2608
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.115
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.289
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 5298 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         13199
_refine_ls_number_restraints     1640
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0777P)^2^+2.1806P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1295
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                12662
_reflns_number_total             13199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00173f2.cif
_cod_data_source_block           hasj160712b
_cod_depositor_comments
'Adding full bibliography for 7706544--7706549.cif.'
_cod_database_code               7706547
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C78H94CaN2O7
_reflns_odcompleteness_completeness 99.94
_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
2. Restrained distances
 O3-C59 \\sim O3-C62 \\sim O6-C74 \\sim O6-C71 \\sim O5-C70 \\sim O5-C67 \\sim
O7A-C78A \\sim O7A-C75A ~
 O4-C63 \\sim O4-C66 \\sim O4A-C63A \\sim O4A-C66A \\sim O5A-C67A \\sim
O5A-C70A \\sim O7-C75 \\sim O7-C78
 \\sim O6A-C71A \\sim O6A-C74A
 with sigma of 0.02
 C70A-C68A \\sim C67A-C69A \\sim C66A-C64A \\sim C65A-C63A \\sim C76-C78 \\sim
C75-C77 \\sim C74A-C72A
 \\sim C71A-C73A
 with sigma of 0.02
 C60A-C59 \\sim C60-C59 \\sim C62-C61A \\sim C62-C61 \\sim C72A-C71A \\sim
C73A-C74A \\sim C72-C71 ~
 C73-C74 \\sim C69-C70 \\sim C69A-C70A \\sim C68A-C67A \\sim C68-C67 \\sim
C65-C66 \\sim C64-C63 \\sim C65A-
 C66A \\sim C63A-C64A \\sim C75A-C76A \\sim C75-C76 \\sim C77-C78 \\sim
C77A-C78A
 with sigma of 0.02
 C61-C60 \\sim C61A-C60A \\sim C73A-C72A \\sim C72-C73 \\sim C68-C69 \\sim
C68A-C69A \\sim C76-C77 ~
 C76A-C77A \\sim C65A-C64A \\sim C64-C65
 with sigma of 0.02
 C61A-C59 \\sim C59-C61 \\sim C60-C62 \\sim C62-C60A \\sim C74-C72 \\sim
C73-C71 \\sim C78A-C76A ~
 C75A-C77A \\sim C63-C65 \\sim C64-C66 \\sim C70-C68 \\sim C67-C69 \\sim
C70A-C68A \\sim C67A-C69A ~
 C71A-C73A \\sim C72A-C74A \\sim C78-C76 \\sim C75-C77 \\sim C63A-C65A \\sim
C66A-C64A
 with sigma of 0.02
 C59-C62 \\sim C75-C78 \\sim C75A-C78A \\sim C71-C74 \\sim C74A-C71A \\sim
C66-C63 \\sim C63A-C66A ~
 C67A-C70A \\sim C67-C70
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O5 \\sim C67 \\sim C68 \\sim C70 \\sim O5A \\sim C67A \\sim C68A \\sim C69A
\\sim C70A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
O4 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim O4A \\sim C63A \\sim C64A
\\sim C65A \\sim C66A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
O7 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim O7A \\sim C75A \\sim C76A
\\sim C77A \\sim C78A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
O6 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim O6A \\sim C71A \\sim C72A
\\sim C73A \\sim C74A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
4. Others
 Sof(O6A)=Sof(C71A)=Sof(H71c)=Sof(H71d)=Sof(C72A)=Sof(H72c)=Sof(H72d)=
 Sof(C73A)=Sof(H73c)=Sof(H73d)=Sof(C74A)=Sof(H74c)=Sof(H74d)=1-FVAR(1)
 Sof(O6)=Sof(C71)=Sof(H71a)=Sof(H71b)=Sof(C72)=Sof(H72a)=Sof(H72b)=Sof(C73)=
 Sof(H73a)=Sof(H73b)=Sof(C74)=Sof(H74a)=Sof(H74b)=FVAR(1)
 Sof(O5A)=Sof(C67A)=Sof(H67c)=Sof(H67d)=Sof(C68A)=Sof(H68c)=Sof(H68d)=
 Sof(C69A)=Sof(H69c)=Sof(H69d)=Sof(C70A)=Sof(H70c)=Sof(H70d)=1-FVAR(2)
 Sof(O5)=Sof(C67)=Sof(H67a)=Sof(H67b)=Sof(C68)=Sof(H68a)=Sof(H68b)=Sof(C69)=
 Sof(H69a)=Sof(H69b)=Sof(C70)=Sof(H70a)=Sof(H70b)=FVAR(2)
 Sof(O4A)=Sof(C63A)=Sof(H63c)=Sof(H63d)=Sof(C64A)=Sof(H64c)=Sof(H64d)=
 Sof(C65A)=Sof(H65c)=Sof(H65d)=Sof(C66A)=Sof(H66c)=Sof(H66d)=1-FVAR(3)
 Sof(O4)=Sof(C63)=Sof(H63a)=Sof(H63b)=Sof(C64)=Sof(H64a)=Sof(H64b)=Sof(C65)=
 Sof(H65a)=Sof(H65b)=Sof(C66)=Sof(H66a)=Sof(H66b)=FVAR(3)
 Sof(H59c)=Sof(H59d)=Sof(H62c)=Sof(H62d)=Sof(C60A)=Sof(H60c)=Sof(H60d)=
 Sof(C61A)=Sof(H61c)=Sof(H61d)=1-FVAR(4)
 Sof(H59a)=Sof(H59b)=Sof(H62a)=Sof(H62b)=Sof(C60)=Sof(H60a)=Sof(H60b)=Sof(C61)=
 Sof(H61a)=Sof(H61b)=FVAR(4)
 Sof(O7A)=Sof(C75A)=Sof(H75c)=Sof(H75d)=Sof(C76A)=Sof(H76c)=Sof(H76d)=
 Sof(C77A)=Sof(H77c)=Sof(H77d)=Sof(C78A)=Sof(H78c)=Sof(H78d)=1-FVAR(5)
 Sof(O7)=Sof(C75)=Sof(H75a)=Sof(H75b)=Sof(C76)=Sof(H76a)=Sof(H76b)=Sof(C77)=
 Sof(H77a)=Sof(H77b)=Sof(C78)=Sof(H78a)=Sof(H78b)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C21(H21), C36(H36)
5.b Secondary CH2 refined with riding coordinates:
 C28(H28a,H28b), C29(H29a,H29b), C43(H43a,H43b), C44(H44a,H44b), C51(H51a,
 H51b), C52(H52a,H52b), C53(H53a,H53b), C54(H54a,H54b), C55(H55a,H55b),
 C56(H56a,H56b), C57(H57a,H57b), C58(H58a,H58b), C59(H59a,H59b), C59(H59c,H59d),
  C62(H62a,H62b), C62(H62c,H62d), C60(H60a,H60b), C61(H61a,H61b), C60A(H60c,
 H60d), C61A(H61c,H61d), C63(H63a,H63b), C64(H64a,H64b), C65(H65a,H65b),
 C66(H66a,H66b), C63A(H63c,H63d), C64A(H64c,H64d), C65A(H65c,H65d), C66A(H66c,
 H66d), C71(H71a,H71b), C72(H72a,H72b), C73(H73a,H73b), C74(H74a,H74b),
 C71A(H71c,H71d), C72A(H72c,H72d), C73A(H73c,H73d), C74A(H74c,H74d), C67(H67a,
 H67b), C68(H68a,H68b), C69(H69a,H69b), C70(H70a,H70b), C67A(H67c,H67d),
 C68A(H68c,H68d), C69A(H69c,H69d), C70A(H70c,H70d), C75(H75a,H75b), C76(H76a,
 H76b), C77(H77a,H77b), C78(H78a,H78b), C75A(H75c,H75d), C76A(H76c,H76d),
 C77A(H77c,H77d), C78A(H78c,H78d)
5.c 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), C23(H23), C24(H24), C25(H25), C26(H26), C31(H31),
  C32(H32), C33(H33), C34(H34), C38(H38), C39(H39), C40(H40), C41(H41),
 C46(H46), C47(H47), C48(H48), C49(H49)
;
_shelx_res_checksum              2400
_shelx_hkl_checksum              66427
_olex2_date_sample_data_collection 2016-07-12
_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 1.124
_oxdiff_exptl_absorpt_empirical_full_min 0.841