A synthetic route to artificial chiral α-amino acids featuring a 3,4-dihydroisoquinolone core through a Rh(III)-catalyzed functionalization of allyl groups in chiral Ni(II) complexes.
Arsenov, Mikhail A.; Stoletova, Nadezhda V.; Smol'yakov, Alexander F.; Savel'yeva, Tat'yana F.; Maleev, Victor I.; Loginov, Dmitry A.; Larionov, Vladimir A.; Organic & biomolecular chemistry 21 (2023) 9143–9149; doi:10.1039/d3ob01513k

data_7159659
_publ_section_title
;
 A synthetic route to artificial chiral &#x3b1;-amino acids featuring a
 3,4-dihydroisoquinolone core through a Rh(III)-catalyzed
 functionalization of allyl groups in chiral Ni(II) complexes.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9143
_journal_page_last               9149
_journal_paper_doi               10.1039/d3ob01513k
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C37 H33 Br N4 Ni O4'
_chemical_formula_sum            'C37 H33 Br N4 Ni O4'
_chemical_formula_weight         736.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-24 deposited with the CCDC.	2023-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.310(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8370(18)
_cell_length_b                   22.263(4)
_cell_length_c                   14.667(2)
_cell_measurement_reflns_used    2217
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.01
_cell_measurement_theta_min      2.30
_cell_volume                     3864.1(11)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1156
_diffrn_reflns_av_unetI/netI     0.3441
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            29687
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.400
_diffrn_reflns_theta_min         1.721
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.576
_exptl_absorpt_correction_T_max  0.2627
_exptl_absorpt_correction_T_min  0.1872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0935 before and 0.0701 after correction.
The Ratio of minimum to maximum transmission is 0.7126.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       needle
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.351
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.125(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.854
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     646
_refine_ls_number_reflns         18182
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      0.854
_refine_ls_R_factor_all          0.2411
_refine_ls_R_factor_gt           0.0703
_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^)+(0.0252P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1422
_refine_ls_wR_factor_ref         0.1916
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.947
_reflns_Friedel_fraction_max     0.884
_reflns_number_gt                5677
_reflns_number_total             18182
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01513k2.cif
_cod_data_source_block           a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7159658--7159659.cif.'
_cod_original_cell_volume        3864.2(11)
_cod_database_code               7159659
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.765
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.875(16)
 0.125(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
3. Restrained distances
 C29A-C28A
 1.55 with sigma of 0.01
 C11A-C12A
 1.43 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C36B) \\sim Ueq, Uanis(C35B) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C1A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C28B) \\sim Ueq, Uanis(C18B) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C14B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C28A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C4A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C30A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N3B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C29A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C5B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C2B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C29B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C31A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25B) = Uanis(C24B) = Uanis(C23B) = Uanis(C22B) = Uanis(C21B) =
Uanis(C20B)
Uanis(C6B) = Uanis(C7B) = Uanis(C8B) = Uanis(C9B) = Uanis(C10B) = Uanis(C11B)
Uanis(C18A) = Uanis(C19A) = Uanis(C14A) = Uanis(C15A) = Uanis(C16A) =
Uanis(C17A)
Uanis(C32A) = Uanis(C37A) = Uanis(C36A) = Uanis(C35A) = Uanis(C34A) =
Uanis(C33A)
5.a Ternary CH refined with riding coordinates:
 C2A(H2AA), C4A(H4A), C27A(H27A), C2B(H2BA), C4B(H4B), C27B(H27B)
5.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C5A(H5AA,H5AB), C28A(H28A,H28B), C29A(H29A,H29B), C30A(H30A,
 H30B), C31A(H31A,H31B), C3B(H3BA,H3BB), C5B(H5BA,H5BB), C28B(H28C,H28D),
 C29B(H29C,H29D), C30B(H30C,H30D), C31B(H31C,H31D)
5.c Aromatic/amide H refined with riding coordinates:
 N2A(H2A), C7A(H7A), C9A(H9A), C10A(H10A), C17A(H17A), C18A(H18A), C19A(H19A),
 C15A(H15A), C16A(H16A), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A),
 C37A(H37A), C36A(H36A), C35A(H35A), C34A(H34A), C33A(H33A), N2B(H2B), C7B(H7B),
  C9B(H9B), C10B(H10B), C18B(H18B), C17B(H17B), C16B(H16B), C15B(H15B),
 C19B(H19B), C22B(H22B), C21B(H21B), C24B(H24B), C23B(H23B), C33B(H33B),
 C34B(H34B), C35B(H35B), C36B(H36B), C37B(H37B)
5.d Fitted hexagon refined as free rotating group:
 C11A(C6A,C7A,C8A,C9A,C10A), C17A(C18A,C19A,C14A,C15A,C16A), C32A(C37A,C36A,
 C35A,C34A,C33A), C7B(C8B,C9B,C10B,C11B,C6B), C18B(C17B,C16B,C15B,C14B,C19B),
 C22B(C21B,C20B,C25B,C24B,C23B), C32B(C33B,C34B,C35B,C36B,C37B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              85536
_shelx_hkl_checksum              26127
_shelx_fab_checksum              9214
_olex2_submission_special_instructions 'No special instructions were received'