A general synthesis of unnatural α-amino acids by iron-catalysed olefin‒olefin coupling via generated radicals
Larionov, Vladimir A.; Stoletova, Nadezhda V.; Kovalev, Vladislav I.; Smol'yakov, Alexander F.; Savel'yeva, Tat'yana F.; Maleev, Victor I.; Organic Chemistry Frontiers 6 (2019) 1094–; doi:10.1039/C9QO00108E

data_1554735
_publ_section_title
;
 A general synthesis of unnatural \a-amino acids by iron-catalysed
 olefin--olefin coupling via generated radicals
;
_journal_issue                   8
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1094
_journal_paper_doi               10.1039/C9QO00108E
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C31 H32 N4 Ni O4, 0.5(C H2 Cl2), 0.5(C Cl4)'
_chemical_formula_sum            'C32 H33 Cl3 N4 Ni O4'
_chemical_formula_weight         702.68
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-22 deposited with the CCDC.	2019-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                81.0080(10)
_cell_angle_beta                 89.6580(10)
_cell_angle_gamma                80.2760(10)
_cell_formula_units_Z            2
_cell_length_a                   9.3743(5)
_cell_length_b                   13.3790(7)
_cell_length_c                   14.9327(8)
_cell_measurement_reflns_used    5116
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.596
_cell_measurement_theta_min      2.20
_cell_volume                     1822.85(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0158
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            17604
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.564
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.790
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6851
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0490 before and 0.0420 after correction. The Ratio of minimum to maximum transmission is 0.9182. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       prism
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.868
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 5681 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.047(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         14086
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0877P)^2^+1.1044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1460
_refine_ls_wR_factor_ref         0.1513
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                12635
_reflns_number_total             14086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00108e2.cif
_cod_data_source_block           b
_cod_database_code               1554735
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.797
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl7S-C3S = Cl8S-C3S = Cl5S-C3S = Cl6S-C3S
 1.72 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(Cl5S) \\sim Ueq, Uanis(Cl6S) \\sim Ueq, Uanis(Cl7S) \\sim Ueq,
Uanis(Cl8S) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uiso(C1S) = Uiso(C2S)
Uanis(Cl7S) = Uanis(Cl8S)
Uanis(Cl5S) = Uanis(Cl6S)
4. Others
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=1-FVAR(1)
 Sof(C2S)=Sof(H2SA)=Sof(H2SB)=FVAR(1)
 Sof(Cl7S)=Sof(Cl6S)=1-FVAR(2)
 Sof(Cl5S)=Sof(Cl8S)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C29B(H29B), C27B(H27C), C28A(H28A), C4A(H4A), C26A(H26A), C4B(H4B)
5.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C28B(H28B,H28C), C27A(H27A,H27B), C6A(H6AA,H6AB), C1B(H1BA,
 H1BB), C3A(H3AA,H3AB), C3B(H3BA,H3BB), C6B(H6BA,H6BB), C2B(H2BA,H2BB),
 C2A(H2AA,H2AB), C1S(H1SA,H1SB), C2S(H2SA,H2SB)
5.c Aromatic/amide H refined with riding coordinates:
 C8A(H8A), C16B(H16B), C25B(H25B), C15A(H15A), C17A(H17A), C12B(H12B),
 C9A(H9A), C16A(H16A), C14B(H14B), C25A(H25A), C8B(H8B), C21A(H21A), C24B(H24B),
  C21B(H21B), C17B(H17B), C24A(H24A), C12A(H12A), C14A(H14A), C11B(H11B),
 C15B(H15B), C10B(H10B), C10A(H10A), C22B(H22B), C22A(H22A), C23B(H23B),
 C11A(H11A), C9B(H9B), C23A(H23A)
5.d X=CH2 refined with riding coordinates:
 N4A(H4AA,H4AB), N4B(H4BA,H4BB)
5.e Idealised Me refined as rotating group:
 C31B(H31A,H31B,H31C), C30A(H30A,H30B,H30C)
;
_shelx_res_checksum              33201
_shelx_hkl_checksum              27474
_shelx_fab_checksum              13650
_olex2_submission_special_instructions 'No special instructions were received'