Enantioselective synthesis of chiral cyclic hydroxylamine ethers <i>via</i> NiH-catalyzed cyclization of alkyne-oxime ethers.
Zhou, Lijin; Fang, Jingjing; Tong, Xiaofeng; Qi, Linjun; Chemical communications (Cambridge, England)  (2026) –; doi:10.1039/d6cc00996d

data_7135728
_publ_section_title
;
 Enantioselective synthesis of chiral cyclic hydroxylamine ethers
 <i>via</i> NiH-catalyzed cyclization of alkyne-oxime ethers.
;
_journal_issue                   32
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8289
_journal_page_last               8292
_journal_paper_doi               10.1039/d6cc00996d
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C18 H19 Br N2 O3 S'
_chemical_formula_sum            'C18 H18 Br N2 O3 S'
_chemical_formula_weight         422.31
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2026-01-21 deposited with the CCDC.	2026-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2550(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.9109(2)
_cell_length_b                   5.45170(10)
_cell_length_c                   16.0369(3)
_cell_measurement_reflns_used    9804
_cell_measurement_temperature    257(2)
_cell_measurement_theta_max      68.29
_cell_measurement_theta_min      4.07
_cell_volume                     949.91(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      257.0
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            29095
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.286
_diffrn_reflns_theta_min         4.069
_exptl_absorpt_coefficient_mu    4.139
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4680
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1409 before and 0.0631 after correction.
The Ratio of minimum to maximum transmission is 0.6214.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_description       block
_exptl_crystal_F_000             430
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.156
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1397 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.035(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3372
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0228
_refine_ls_R_factor_gt           0.0224
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0350P)^2^+0.1078P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0610
_refine_ls_wR_factor_ref         0.0614
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    0.933
_reflns_Friedel_fraction_max     0.932
_reflns_number_gt                3308
_reflns_number_total             3372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00996d2.cif
_cod_data_source_block           1
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_absolute_configuration' value 'RM' was changed
to 'rm' 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 7135728.cif.
;
_cod_database_code               7135728
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.477
_shelx_estimated_absorpt_t_min   0.449
_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.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C17(H17), C18(H18), C1(H1A), C14(H14), C15(H15), C5(H5), C4(H4),
 C2(H2), C3(H3)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              57813
_shelx_hkl_checksum              26131
_olex2_submission_special_instructions 'No special instructions were received'