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_7706546
_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         'C54 H50 Ca N2 O2, C7 H8'
_chemical_formula_sum            'C61 H58 Ca N2 O2'
_chemical_formula_weight         891.17
_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                   15.21280(10)
_cell_length_b                   15.60600(10)
_cell_length_c                   20.6921(2)
_cell_measurement_reflns_used    30472
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.5310
_cell_measurement_theta_min      3.5320
_cell_volume                     4912.53(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(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 0.990
_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    -64.00  31.00   1.00    4.50    --  -41.69  38.00-180.00   95
  2  \w   -116.00 -10.00   1.00    4.50    --  -41.69 -77.00 -90.00  106
  3  \w    -68.00  28.00   1.00    4.50    --  -41.69  57.00 -60.00   96
  4  \w   -112.00 -15.00   1.00    4.50    --  -41.69 -57.00 150.00   97
  5  \w     19.00 114.00   1.00    4.50    --   41.69  38.00  90.00   95
  6  \w     61.00 178.00   1.00   18.00    --  106.00  15.00 150.00  117
  7  \w     75.00 178.00   1.00   18.00    --  106.00  77.00 -60.00  103
  8  \w     75.00 178.00   1.00   18.00    --  106.00  77.00-150.00  103
  9  \w     82.00 177.00   1.00   18.00    --  106.00  45.00  60.00   95
 10  \w     25.00 109.00   1.00   18.00    --  106.00 -94.00-120.00   84
 11  \w     35.00 130.00   1.00   18.00    --  106.00 -45.00-120.00   95
 12  \w     82.00 177.00   1.00   18.00    --  106.00  45.00 -90.00   95
 13  \w     26.00 151.00   1.00   18.00    --  106.00 -15.00 120.00  125
 14  \w   -112.00 -15.00   1.00    4.50    --  -41.69 -57.00   0.00   97
 15  \w   -116.00 -10.00   1.00    4.50    --  -41.69 -77.00  90.00  106
 16  \w     23.00  97.00   1.00    4.50    --   41.69-125.00-150.00   74
 17  \w      1.00  82.00   1.00    4.50    --   41.69 -99.00  30.00   81
 18  \w     78.00 176.00   1.00   18.00    --  106.00  61.00-180.00   98
 19  \w     25.00 109.00   1.00   18.00    --  106.00 -94.00  60.00   84
;
_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      0.0990624000
_diffrn_orient_matrix_UB_12      -0.0117275000
_diffrn_orient_matrix_UB_13      0.0125704000
_diffrn_orient_matrix_UB_21      -0.0190382000
_diffrn_orient_matrix_UB_22      -0.0839760000
_diffrn_orient_matrix_UB_23      0.0365930000
_diffrn_orient_matrix_UB_31      0.0087739000
_diffrn_orient_matrix_UB_32      -0.0505231000
_diffrn_orient_matrix_UB_33      -0.0636300000
_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  0.0566
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            54293
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.876
_diffrn_reflns_theta_min         4.058
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.447
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.844
_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    1.205
_exptl_crystal_description       block
_exptl_crystal_F_000             1896
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.582
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 4014 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     633
_refine_ls_number_reflns         9770
_refine_ls_number_restraints     229
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0660P)^2^+0.3963P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1004
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                9438
_reflns_number_total             9770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt00173f2.cif
_cod_data_source_block           hasj160726b
_cod_depositor_comments
'Adding full bibliography for 7706544--7706549.cif.'
_cod_database_code               7706546
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C61H58CaN2O2
_reflns_odcompleteness_completeness 99.96
_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. Restrained distances
 O2-C54 \\sim O2-C54A \\sim O2-C51 \\sim O2-C51A
 with sigma of 0.02
 C52A-C53A \\sim C52-C53
 with sigma of 0.02
 C52A-C51A \\sim C52-C51 \\sim C53-C54 \\sim C53A-C54A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O2 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C51A \\sim C52A \\sim C53A
\\sim C54A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
4. Others
 Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=
 Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54C)=Sof(H54D)=1-FVAR(1)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C21(H21), C34(H34)
5.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C51A(H51C,H51D),
 C52A(H52C,H52D), C53A(H53C,H53D), C54A(H54C,H54D)
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), C27(H27),
  C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C36(H36), C37(H37),
 C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C56(H56), C57(H57), C58(H58), C59(H59), C60(H60)
5.d Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C)
;
_shelx_res_checksum              93534
_shelx_hkl_checksum              32837
_olex2_date_sample_data_collection 2016-07-26
_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 1.406
_oxdiff_exptl_absorpt_empirical_full_min 0.775