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_7159989
_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 syn
_chemical_formula_moiety         'C12 H16 N2 O5 S'
_chemical_formula_sum            'C12 H16 N2 O5 S'
_chemical_formula_weight         300.33
_chemical_name_systematic        SJG_DK_03_273
_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             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                 98.887(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2670(15)
_cell_length_b                   5.7556(6)
_cell_length_c                   11.9973(14)
_cell_measurement_reflns_used    4573
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      26.0490
_cell_measurement_theta_min      1.6800
_cell_volume                     700.44(15)
_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  'ShelXL (Sheldrick, 2015)'
_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     -9.73 182.27   1.00   10.00   6.61  -9.84 -31.50    --   192
  2  \w    -65.46  -0.46   1.00   10.00    --  -19.34  94.56 145.16   65
  3  \w   -100.81  15.19   1.00   10.00    --   -9.84 -59.25-123.92  116
  4  \w    -65.46  -0.46   1.00   10.00    --  -19.34  94.56  73.16   65
  5  \w   -100.81  15.19   1.00   10.00    --   -9.84 -59.25 -51.92  116
  6  \w    -65.46  -0.46   1.00   10.00    --  -19.34  94.56   1.16   65
;
_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      0.0696928000
_diffrn_orient_matrix_UB_12      0.0101312000
_diffrn_orient_matrix_UB_13      0.0093024000
_diffrn_orient_matrix_UB_21      -0.0009969000
_diffrn_orient_matrix_UB_22      0.0166117000
_diffrn_orient_matrix_UB_23      0.0584141000
_diffrn_orient_matrix_UB_31      0.0056397000
_diffrn_orient_matrix_UB_32      -0.1217214000
_diffrn_orient_matrix_UB_33      0.0087182000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1768
_diffrn_reflns_av_unetI/netI     0.0999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10871
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         1.718
_diffrn_source                   'sealed tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.252
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66061
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_preparation       DCM
_exptl_crystal_recrystallization_method DCM
_exptl_crystal_size_max          0.64
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.436
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Flack x determined using 584 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         2458
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0976
_refine_ls_R_factor_gt           0.0842
_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^)+(0.1469P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2061
_refine_ls_wR_factor_ref         0.2311
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                1971
_reflns_number_total             2458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00855c2.cif
_cod_data_source_block           sjg_dk_03_273_autored
_cod_depositor_comments
'Adding full bibliography for 7159988--7159989.cif.'
_cod_database_code               7159989
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.855
_reflns_odcompleteness_completeness 84.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     37.11
_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:
 C00D(H00D), C00H(H00J)
2.b Secondary CH2 refined with riding coordinates:
 C00A(H00A,H00B), C00J(H00L,H00M)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00C), C00F(H00H), C00G(H00I), C00I(H00K)
2.d Idealised Me refined as rotating group:
 C00E(H00E,H00F,H00G), C00K(H00N,H00O,H00P)
;
_shelx_res_checksum              20215
_olex2_exptl_crystal_mounting_method SOLID
_olex2_submission_original_sample_id SJG_DK_03_273
_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 2.356
_oxdiff_exptl_absorpt_empirical_full_min 0.512