Deciphering substitution effects on reductive hydroalkoxylation of alkynyl aminols for stereoselective synthesis of morpholines and 1,4-oxazepanes: total synthesis of tridemorph and fenpropimorph.
Gharpure, Santosh J.; Kalita, Deepika; Somani, Shipra; Pal, Juhi; Organic & biomolecular chemistry 22 (2024) 5529–5533; doi:10.1039/d4ob00855c

data_7159988
_publ_section_title
;
 Deciphering substitution effects on reductive hydroalkoxylation of
 alkynyl aminols for stereoselective synthesis of morpholines and
 1,4-oxazepanes: total synthesis of tridemorph and fenpropimorph.
;
_journal_issue                   27
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5529
_journal_page_last               5533
_journal_paper_doi               10.1039/d4ob00855c
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H25 N O3 S'
_chemical_formula_sum            'C20 H25 N O3 S'
_chemical_formula_weight         359.47
_chemical_name_systematic        SJG_DK_7_MEMB_TMS
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-18
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2024-05-19 deposited with the CCDC.	2024-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.8103(7)
_cell_length_b                   13.6493(13)
_cell_length_c                   17.9317(14)
_cell_measurement_reflns_used    948
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      18.5020
_cell_measurement_theta_min      1.8490
_cell_volume                     1911.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f   -117.00   9.00   1.00    3.00 -16.27   0.00  31.50    --   126
  2  \w    -90.96  25.04   1.00    3.00    --    0.00 -59.25 -51.92  116
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0224222000
_diffrn_orient_matrix_UB_12      0.0355685000
_diffrn_orient_matrix_UB_13      0.0271500000
_diffrn_orient_matrix_UB_21      0.0847956000
_diffrn_orient_matrix_UB_22      0.0011177000
_diffrn_orient_matrix_UB_23      -0.0141221000
_diffrn_orient_matrix_UB_31      -0.0234460000
_diffrn_orient_matrix_UB_32      0.0378896000
_diffrn_orient_matrix_UB_33      -0.0250626000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1234
_diffrn_reflns_av_unetI/netI     0.0929
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            14713
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.988
_diffrn_reflns_theta_max         24.988
_diffrn_reflns_theta_min         1.875
_diffrn_source                   'sealed tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.187
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24152
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             768
_exptl_crystal_preparation       DCM
_exptl_crystal_recrystallization_method DCM
_exptl_crystal_size_max          0.65
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.225
_refine_diff_density_min         -0.373
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 785 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3368
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.0840
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0518P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1367
_reflns_Friedel_coverage         0.732
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2491
_reflns_number_total             3368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00855c2.cif
_cod_data_source_block           sjg_dk_7_memb_tms_autored
_cod_depositor_comments
'Adding full bibliography for 7159988--7159989.cif.'
_cod_database_code               7159988
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.888
_reflns_odcompleteness_completeness 90.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.41
_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:
 C00B(H00B), C00K(H00M)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00C,H00D), C00G(H00G,H00H), C00H(H00I,H00J), C00L(H00N,H00O)
2.c Aromatic/amide H refined with riding coordinates:
 C006(H006), C007(H007), C00A(H00A), C00E(H00E), C00F(H00F), C00I(H00K),
 C00J(H00L), C00M(H00P), C00O(H00T)
2.d Idealised Me refined as rotating group:
 C00N(H00Q,H00R,H00S), C00P(H00U,H00V,H00W)
;
_shelx_res_checksum              6295
_olex2_exptl_crystal_mounting_method SOLID
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.842
_oxdiff_exptl_absorpt_empirical_full_min 0.391