Chemo-, Regio-, and Enantioselective Synthesis of Allylic Nitrones via Rhodium-Catalyzed Addition of Oximes to Allenes
Breit, Bernhard; Wang, Yu-Hsuan; Chemical Communications  (2019) –; doi:10.1039/C9CC03391B

data_7123587
_publ_section_title
;
 Chemo-, Regio-, and Enantioselective Synthesis of Allylic Nitrones via
 Rhodium-Catalyzed Addition of Oximes to Allenes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03391B
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H25 N O3 S'
_chemical_formula_sum            'C25 H25 N O3 S'
_chemical_formula_weight         419.52
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-04-04 deposited with the CCDC.    2019-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.992(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.244(3)
_cell_length_b                   8.741(4)
_cell_length_c                   15.818(6)
_cell_measurement_reflns_used    3838
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.620
_cell_measurement_theta_min      2.686
_cell_volume                     1101.1(8)
_computing_cell_refinement       'SAINT V8.38A (Madison, 2016)'
_computing_data_collection       'Bruker APEX2 software'
_computing_data_reduction        'SAINT V8.38A (Madison, 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      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_device       'fixed-chi two circle goniometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0181
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            6162
_diffrn_reflns_point_group_measured_fraction_full 0.723
_diffrn_reflns_point_group_measured_fraction_max 0.682
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.453
_diffrn_reflns_theta_min         1.333
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           50
_diffrn_source_type              'Incoatec Mo I\ms'
_diffrn_source_voltage           0.6
_exptl_absorpt_coefficient_mu    0.173
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6934
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1219 before and 0.0258 after correction. The Ratio of minimum to maximum transmission is 0.9300. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of ethyl acetate and propyl acetate by slow evaporation'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 819 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         3445
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0307P)^2^+0.2944P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0688
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.338
_reflns_Friedel_fraction_full    0.431
_reflns_Friedel_fraction_max     0.369
_reflns_number_gt                3331
_reflns_number_total             3445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03391b2.cif
_cod_data_source_block           breit_sh2268_0m_a
_cod_original_cell_volume        1101.0(8)
_cod_database_code               7123587
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C6(H6), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
;
_shelx_res_checksum              4539
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems 800'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'