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_7159658
_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         'C12 H13 Cl N2 O3'
_chemical_formula_sum            'C12 H13 Cl N2 O3'
_chemical_formula_weight         268.69
_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             2023-07-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-03 deposited with the CCDC.	2023-11-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.93(2)
_cell_angle_gamma                90
_cell_formula_units_Z            6
_cell_length_a                   21.160(8)
_cell_length_b                   5.022(2)
_cell_length_c                   21.185(8)
_cell_measurement_reflns_used    1560
_cell_measurement_temperature    120
_cell_measurement_theta_max      22.26
_cell_measurement_theta_min      2.22
_cell_volume                     1951.0(14)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.976
_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  0.1521
_diffrn_reflns_av_unetI/netI     0.3531
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            14255
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.923
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.295
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.5217
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1501 before and 0.0870 after correction.
The Ratio of minimum to maximum transmission is 0.6994.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description       plate
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.738
_refine_diff_density_min         -0.659
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.31(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     490
_refine_ls_number_reflns         7223
_refine_ls_number_restraints     175
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.2453
_refine_ls_R_factor_gt           0.1480
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0362P)^2^+11.6301P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2933
_refine_ls_wR_factor_ref         0.3466
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    0.917
_reflns_Friedel_fraction_max     0.901
_reflns_number_gt                3302
_reflns_number_total             7223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01513k2.cif
_cod_data_source_block           a
_cod_depositor_comments
'Adding full bibliography for 7159658--7159659.cif.'
_cod_database_code               7159658
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C8B) \\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(N2B) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq,
Uanis(C8A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C7C) \\sim Ueq, Uanis(C6C)
\\sim Ueq, Uanis(N1C) \\sim Ueq, Uanis(C10C) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C11C) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C3B) \\sim Ueq, Uanis(C2B) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(N2C)
\\sim Ueq, Uanis(C4C) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.002
Uanis(C9B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C12B) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(C2C)
\\sim Ueq, Uanis(C8C) \\sim Ueq, Uanis(C9C) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(O1B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C7B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O2C) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3.a Ternary CH refined with riding coordinates:
 C2A(H2AA), C4A(H4A), C2B(H2BA), C4B(H4B), C2C(H2CA), C4C(H4C)
3.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C5A(H5AA,H5AB), C3B(H3BA,H3BB), C5B(H5BA,H5BB), C3C(H3CA,
 H3CB), C5C(H5CA,H5CB)
3.c Aromatic/amide H refined with riding coordinates:
 N2A(H2A), C7A(H7A), C9A(H9A), C10A(H10A), N2B(H2B), C7B(H7B), C9B(H9B),
 C10B(H10B), N2C(H2C), C7C(H7C), C9C(H9C), C10C(H10C)
3.d Idealised Me refined as rotating group:
 N1A(H1AA,H1AB,H1AC), N1B(H1BA,H1BB,H1BC), N1C(H1CA,H1CB,H1CC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25434
_shelx_hkl_checksum              65266
_shelx_fab_checksum              91133
_olex2_submission_special_instructions 'No special instructions were received'