Deprotective Lossen rearrangement: a direct and general transformation of Nms-amides to unsymmetrical ureas.
Spieß, Philipp; Brześkiewicz, Jakub; Maulide, Nuno; Chemical science 15 (2024) 15799–15803; doi:10.1039/d4sc04974h

data_1572561
_publ_section_title
;
 Deprotective Lossen rearrangement: a direct and general transformation of
 Nms-amides to unsymmetrical ureas.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              15799
_journal_page_last               15803
_journal_paper_doi               10.1039/d4sc04974h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_sum            'C14 H16 N2 O2'
_chemical_formula_weight         244.29
_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_cell_setting           orthorhombic
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-08
_audit_creation_method           'STOE LANA'
_audit_update_record
;
2023-06-09 deposited with the CCDC.	2024-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8956(5)
_cell_length_b                   10.1319(5)
_cell_length_c                   11.9988(9)
_cell_measurement_reflns_used    26059
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.79
_cell_measurement_theta_min      2.67
_cell_volume                     1203.01(12)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)
;
_computing_data_reduction
'  X-Area Integrate 2.5.3.0 (STOE, 2021)  X-Area LANA 2.7.5.0 (STOE, 2022)'
_computing_molecular_graphics    'ShelXle (H\"ubschle 2011)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.1, Darmstadt 2022
;
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'EIGER2 500K'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details      ' 1641 frames, detector distance = 40 mm'
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14507
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.72
_diffrn_reflns_theta_min         2.67
_diffrn_source                   'Axo Mo'
_diffrn_source_current           0.830
_diffrn_source_power             0.050
_diffrn_source_voltage           60
_exptl_absorpt_coefficient_mu    0.091
_exptl_absorpt_correction_T_max  0.9970
_exptl_absorpt_correction_T_min  0.9904
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
STOE LANA, spherical absorption correction
;
_exptl_crystal_colour            clear
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'orthorhombic brick'
_exptl_crystal_F_000             520
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Acetone'
_exptl_crystal_size_max          0.480
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.150
_exptl_crystal_size_rad          0.145
_refine_diff_density_max         0.241
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1043 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         3565
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0399P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0813
_refine_ls_wR_factor_ref         0.0825
_reflns_d_resolution_high        0.696
_reflns_d_resolution_low         7.634
_reflns_Friedel_coverage         0.718
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.926
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              14
_reflns_limit_k_min              -14
_reflns_limit_l_max              16
_reflns_limit_l_min              -17
_reflns_number_gt                2861
_reflns_number_total             3565
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04974h2.cif
_cod_data_source_block           PHSP1070_a
_cod_depositor_comments
'Adding full bibliography for 1572561--1572562.cif.'
_cod_database_code               1572561
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'J. Richter'
_stoe_detector_size_x            '7.7 cm'
_stoe_detector_size_y            '3.8 cm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_distance          '40.0 mm'
_stoe_measurement_identifier     PHSP1070
_stoe_measurement_tube_power     '49.8 W'
_stoe_measurement_total_run_number 21
_stoe_measurement_total_frame_number 1641
_stoe_measurement_min_exposure_per_frame '4.0 s'
_stoe_measurement_max_exposure_per_frame '4.0 s'
_stoe_measurement_mean_exposure_per_frame '4.0 s'
_stoe_measurement_total_exposure_time '109 min'
_stoe_evaluation_integration_a   15.0
_stoe_evaluation_integration_b   1.5
_stoe_evaluation_integration_ems 0.040
_stoe_evaluation_lana_point_group 222
_stoe_evaluation_lana_fs_max_order -
_stoe_evaluation_lana_dxs_max_order -
_stoe_evaluation_lana_dys_max_order -
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max -
_stoe_evaluation_lana_bos_l_odd_max -
_stoe_evaluation_lana_or_c1      0.050
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      1.0
_stoe_evaluation_lana_max_2theta_available 61.5
_stoe_evaluation_lana_max_2theta_desired 61.5
_stoe_evaluation_lana_number_refls_total 15923
_stoe_evaluation_lana_number_refls_outliers 1332
_stoe_evaluation_lana_number_refls_after_or 14591
_stoe_evaluation_lana_number_refls_unique 3583
_stoe_evaluation_lana_number_refls_written 14591
_stoe_evaluation_lana_completeness 94.9
_stoe_evaluation_lana_mean_redundancy 4.1
_stoe_evaluation_lana_table
;
2Theta           7.8   14.2   20.6   27.0   33.4   39.8   46.2   52.6   59.0
<Resolution>    4.47   2.78   1.96   1.54   1.23   1.04   0.90   0.80   0.73
N(total)         214    996   2069   2076   1958   2170   2411   2306   1723
<Redundancy>     6.8   11.5   11.9    7.0    4.6    3.9    3.5    2.8    2.4
Complet. [%%]   100.0  100.0  100.0  100.0   99.7   99.8   99.7   97.3   81.1
<I/sigma>      212.9  100.4   53.2   27.0   17.0   11.3    5.6    3.5    2.9
R(int)         0.072  0.083  0.060  0.042  0.037  0.043  0.066  0.081  0.091
;
_shelx_estimated_absorpt_t_min   0.957
_shelx_estimated_absorpt_t_max   0.986
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              27660
_shelx_hkl_checksum              64341