Deoxygenative dual CO2 conversions: methylenation and switchable N-formylation/N-methylation of tryptamines
Takaishi, Kazuto; Morishita, Hajime; Iwaki, Kosuke; Ema, Tadashi; Green Chemistry 27 (2025) 5359–5365; doi:10.1039/D5GC00942A

data_7250271
_publ_section_title
;
 Deoxygenative dual CO2 conversions: methylenation and switchable
 N-formylation/N-methylation of tryptamines
;
_journal_issue                   18
_journal_name_full               'Green Chemistry'
_journal_page_first              5359
_journal_page_last               5365
_journal_paper_doi               10.1039/D5GC00942A
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C12 H12 N2 O'
_chemical_formula_sum            'C12 H12 N2 O'
_chemical_formula_weight         200.24
_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             2023-01-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-28 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0306(3)
_cell_length_b                   10.3023(6)
_cell_length_c                   16.1959(10)
_cell_measurement_reflns_used    8780
_cell_measurement_temperature    200
_cell_measurement_theta_max      29.4750
_cell_measurement_theta_min      2.3310
_cell_volume                     1006.24(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.962
_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   -105.00  75.00   0.50    1.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00 180.00  360
  4  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00 270.00  360
;
_diffrn_measurement_device       'AFC11 SATURN724+ Right'
_diffrn_measurement_device_type  'Rigaku Varimax with Saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0638116000
_diffrn_orient_matrix_UB_12      -0.0447543000
_diffrn_orient_matrix_UB_13      0.0232501000
_diffrn_orient_matrix_UB_21      0.0981794000
_diffrn_orient_matrix_UB_22      0.0238864000
_diffrn_orient_matrix_UB_23      -0.0187368000
_diffrn_orient_matrix_UB_31      0.0110255000
_diffrn_orient_matrix_UB_32      0.0465392000
_diffrn_orient_matrix_UB_33      0.0320436000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0768
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21034
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.761
_diffrn_reflns_theta_min         2.343
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'MicroMax 007'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90957
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.161
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 635 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.1(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         2943
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1013
_refine_ls_R_factor_gt           0.0600
_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^)+(0.0490P)^2^+0.1289P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1205
_reflns_Friedel_coverage         0.679
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.904
_reflns_number_gt                2071
_reflns_number_total             2943
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc00942a2.cif
_cod_data_source_block           takaishi_autored
_cod_depositor_comments
'Adding full bibliography for 7250271--7250272.cif.'
_cod_database_code               7250271
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         O1N2C15H15
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.987
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C12(H12)
;
_shelx_res_checksum              42084
_shelx_hkl_checksum              48240
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.150
_oxdiff_exptl_absorpt_empirical_full_min 0.861