Diastereoselective arylation of bis-lactim ethers catalyzed by <i>N</i>-coordinating ylide-functionalized phosphine (NYPhos).
Sowa Prendes, Daniel; Löffler, Julian; Barreto, Ivan Martins; Sankaran, Nagesh; Remm, Henning; Nascimento de Oliveira, Ronaldo; Gessner, Viktoria H.; Gooßen, Lukas J; Chemical science 16 (2025) 14152–14160; doi:10.1039/d5sc02814k

data_1574991
_publ_section_title
;
 Diastereoselective arylation of bis-lactim ethers catalyzed by
 <i>N</i>-coordinating ylide-functionalized phosphine (NYPhos).
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              14152
_journal_page_last               14160
_journal_paper_doi               10.1039/d5sc02814k
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         '2(C16 H22 N2 O3)'
_chemical_formula_sum            'C32 H44 N4 O6'
_chemical_formula_weight         580.729
_chemical_name_systematic
(2S,5R)-2-isopropyl-3,6-dimethoxy-5-(4-methoxyphenyl)-2,5-dihydropyrazine
_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'
_symmetry_Int_Tables_number      19
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-04-12 deposited with the CCDC.	2025-06-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.8893(2)
_cell_length_b                   9.6176(2)
_cell_length_c                   41.2385(7)
_cell_measurement_reflns_used    7724
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      76.8540
_cell_measurement_theta_min      4.2710
_cell_volume                     3129.02(12)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9988
_diffrn_measured_fraction_theta_max 0.9235
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     43.00  68.00   0.50    0.43    --  105.91 -61.00   0.00   50
  2  \w     33.00  96.00   0.50    0.43    --  105.91 -94.00 -90.00  126
  3  \w     50.00  97.00   0.50    0.43    --  105.91 -94.00-120.00   94
  4  \w     63.00  90.00   0.50    0.11    --   47.28-138.00-121.00   54
  5  \w    -40.00   7.00   0.50    0.11    --  -47.28  38.00 150.00   94
  6  \w    -46.00 -21.00   0.50    0.43    --  -91.75  45.00 150.00   50
  7  \w    -53.00 -27.00   0.50    0.43    --  -91.75  55.00-107.00   52
  8  \w    -48.00 -22.00   0.50    0.43    --  -91.75  45.00-180.00   52
  9  \w    -87.00 -28.00   0.50    0.43    --  -91.75 138.00 -59.00  118
 10  \w    -77.00 -21.00   0.50    0.43    --  -91.75 131.00 124.00  112
 11  \w   -130.00 -75.00   0.50    0.43    --  -91.75 -65.00 -69.00  110
 12  \w   -117.00 -92.00   0.50    0.11    --  -47.28-125.00-120.00   50
 13  \w   -110.00 -73.00   0.50    0.11    --  -47.28-125.00 -90.00   74
 14  \w   -119.00 -79.00   0.50    0.11    --  -47.28-125.00  60.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0017493000
_diffrn_orient_matrix_UB_12      -0.1200850000
_diffrn_orient_matrix_UB_13      0.0247272000
_diffrn_orient_matrix_UB_21      0.1951747000
_diffrn_orient_matrix_UB_22      0.0037282000
_diffrn_orient_matrix_UB_23      0.0005068000
_diffrn_orient_matrix_UB_31      -0.0049854000
_diffrn_orient_matrix_UB_32      0.1058920000
_diffrn_orient_matrix_UB_33      0.0280149000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.9988
_diffrn_reflns_Laue_measured_fraction_max 0.9235
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            12503
_diffrn_reflns_point_group_measured_fraction_full 0.9003
_diffrn_reflns_point_group_measured_fraction_max 0.8120
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         76.88
_diffrn_reflns_theta_min         4.29
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.693
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.06843
_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 yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.233
_exptl_crystal_description       block
_exptl_crystal_F_000             1252.237
_exptl_crystal_recrystallization_method 'evaporation of n-hexane'
_exptl_crystal_size_max          0.578
_exptl_crystal_size_mid          0.347
_exptl_crystal_size_min          0.252
_refine_diff_density_max         0.3698
_refine_diff_density_min         -0.2523
_refine_diff_density_rms         0.0547
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.04(12)
_refine_ls_d_res_high            0.7916
_refine_ls_d_res_low             10.3096
_refine_ls_goodness_of_fit_ref   1.0273
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    68
_refine_ls_number_parameters     389
_refine_ls_number_reflns         5357
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0273
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0482
_refine_ls_shift/su_max          -0.0005
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0886P)^2^+0.6399P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1298
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.663
_reflns_limit_h_max              9
_reflns_limit_h_min              -9
_reflns_limit_k_max              11
_reflns_limit_k_min              -11
_reflns_limit_l_max              50
_reflns_limit_l_min              -50
_reflns_number_gt                4963
_reflns_number_total             5357
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc02814k6.cif
_cod_data_source_block           prd1388_auto
_cod_depositor_comments
'Adding full bibliography for 1574991--1574993.cif.'
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               1574991
_chemical_oxdiff_formula         C16H22N2O3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C25(H25), C22(H22), C40(H40), C19(H19)
2.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C8(H8), C32(H32), C9(H9), C30(H30), C12(H12), C33(H33), C11(H11)
2.c Idealised Me refined as rotating group:
 C35(H35a,H35b,H35c), C42(H42a,H42b,H42c), C18(H18a,H18b,H18c), C14(H14a,H14b,
 H14c), C39(H39a,H39b,H39c), C16(H16a,H16b,H16c), C41(H41a,H41b,H41c), C21(H21a,
 H21b,H21c), C20(H20a,H20b,H20c), C37(H37a,H37b,H37c)
;
_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 7.244
_oxdiff_exptl_absorpt_empirical_full_min 0.264