Access to distal biaxial atropisomers by iridium catalyzed asymmetric C-H alkylation.
Hu, Xueqing; Zhao, Yunxu; He, Tong; Niu, Caoyue; Liu, Feipeng; Jia, Wei; Mu, Yi; Li, Xingwei; Rong, Zi-Qiang; Chemical science 15 (2024) 13541–13549; doi:10.1039/d4sc01837k

data_1572155
_publ_section_title
;
 Access to distal biaxial atropisomers by iridium catalyzed asymmetric C-H
 alkylation.
;
_journal_issue                   33
_journal_name_full               'Chemical science'
_journal_page_first              13541
_journal_page_last               13549
_journal_paper_doi               10.1039/d4sc01837k
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C41 H33 N3 O4, C4 H8 O2'
_chemical_formula_sum            'C45 H41 N3 O6'
_chemical_formula_weight         719.81
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-22 deposited with the CCDC.	2024-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0009(5)
_cell_length_b                   11.0174(6)
_cell_length_c                   34.0362(18)
_cell_measurement_reflns_used    9408
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      68.040
_cell_measurement_theta_min      4.609
_cell_volume                     3750.2(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            59003
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.429
_diffrn_reflns_theta_min         4.218
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.684
_exptl_absorpt_correction_T_max  0.3201
_exptl_absorpt_correction_T_min  0.1845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1736 before and 0.1032 after correction.
The Ratio of minimum to maximum transmission is 0.5764.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       block
_exptl_crystal_F_000             1520
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.727
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 2754 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(7)
_refine_ls_extinction_coef       0.0027(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     602
_refine_ls_number_reflns         6840
_refine_ls_number_restraints     285
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.0575
_refine_ls_R_factor_gt           0.0557
_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^)+(0.1213P)^2^+0.4082P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1536
_refine_ls_wR_factor_ref         0.1570
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                6538
_reflns_number_total             6840
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01837k2.cif
_cod_data_source_block           cu_20231118_ys_rzq_zyx1_138_1_
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_absolute_configuration' value 'AD' was changed
to 'ad' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1572152--1572155.cif.
;
_cod_database_code               1572155
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.916
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H2 of C2, H5 of C5, H6 of C6, H1 of C1, H4 of C4, H17 of
  C17, H37 of C37, H26 of C26, H25 of C25, H12 of C12, H34 of C34, H38 of C38,
  H39 of C39, H40 of C40, H15 of C15, H18 of C18, H14 of C14, H24 of C24, H7 of
  C7, H20 of C20, H13 of C13, H22 of C22, H41 of C41
 At 1.5 times of:
  All C(H,H,H) groups, H42A of C42B, All C(H,H,H,H,H) groups
2. Restrained distances
 O6A-C43A
 1.32 with sigma of 0.02
 C44B-C45B
 1.5 with sigma of 0.02
 C42A-C43A
 1.49 with sigma of 0.02
 C42B-C43B
 1.49 with sigma of 0.02
 O5A-C43A
 1.22 with sigma of 0.02
 O6A-C44A
 1.46 with sigma of 0.02
 C44A-C45A
 1.5 with sigma of 0.02
 O6-C43
 1.32 with sigma of 0.02
 O6-C44
 1.46 with sigma of 0.02
 O5-C43
 1.22 with sigma of 0.02
 C42-C43
 1.49 with sigma of 0.02
 C44-C45
 1.5 with sigma of 0.02
 O6B-C43B
 1.32 with sigma of 0.02
 O6B-C44B
 1.46 with sigma of 0.02
 O5B-C43B
 1.22 with sigma of 0.02
 O6B-C42B
 2.35 with sigma of 0.04
 O6B-C45B
 2.38 with sigma of 0.04
 O6A-C42A
 2.35 with sigma of 0.04
 O5B-C42B
 2.4 with sigma of 0.04
 O6A-O5A
 2.24 with sigma of 0.04
 O5A-C42A
 2.4 with sigma of 0.04
 O6A-C45A
 2.38 with sigma of 0.04
 O6-O5
 2.24 with sigma of 0.04
 O6-C42
 2.35 with sigma of 0.04
 O6-C45
 2.38 with sigma of 0.04
 O5-C42
 2.4 with sigma of 0.04
 O6B-O5B
 2.24 with sigma of 0.04
 C42B-C43B \\sim C44B-C45B
 with sigma of 0.02
 C42A-C43A \\sim C44A-C45A
 with sigma of 0.02
 C42-C43 \\sim C44-C45
 with sigma of 0.02
3. Restrained planarity
 O5B, O6B, C42B, C43B, C44B, C45B
 with sigma of 0.1
 O5A, O6A, C42A, C43A, C44A, C45A
 with sigma of 0.1
 O5, O6, C42, C43, C44, C45
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O5 \\sim O5A \\sim O5B \\sim O6 \\sim O6A \\sim O6B \\sim C42 \\sim C42A \\sim
C42B \\sim C43 \\sim C43B \\sim C44 \\sim C44B \\sim C45 \\sim C45A \\sim C45B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C43) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: C42B(0.25) H42A(0.25) O5(0.4) O5A(0.35) O5B(0.25) O6(0.4)
 O6A(0.35) O6B(0.25) C42(0.4) H42D(0.4) H42E(0.4) H42F(0.4) C42A(0.35)
 H42G(0.35) H42H(0.35) H42I(0.35) H42B(0.25) H42C(0.25) C43(0.4) C43A(0.35)
 C43B(0.25) C44(0.4) H44C(0.4) H44D(0.4) C44A(0.35) H44E(0.35) H44F(0.35)
 C44B(0.25) H44A(0.25) H44B(0.25) C45(0.4) H45D(0.4) H45E(0.4) H45F(0.4)
 C45A(0.35) H45G(0.35) H45H(0.35) H45I(0.35) C45B(0.25) H45A(0.25) H45B(0.25)
 H45C(0.25)
6.a Everything fixed:
 H42A, H42B, H42C, H45A, H45B, H45C
6.b Ternary CH refined with riding coordinates:
 C20(H20), C22(H22), C24(H24), C25(H25), C26(H26)
6.c Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C23(H23A,H23B), C44(H44C,H44D), C44A(H44E,H44F), C44B(H44A,
 H44B)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C34(H34), C37(H37), C38(H38), C39(H39), C40(H40),
  C41(H41)
6.e Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C33(H33A,H33B,H33C), C42(H42D,H42E,H42F), C42A(H42G,H42H,
 H42I), C45(H45D,H45E,H45F), C45A(H45G,H45H,H45I)
;
_shelx_res_checksum              6541
_shelx_hkl_checksum              15453
_olex2_submission_special_instructions 'No special instructions were received'