Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl Amines by CO<sub>2</sub>-Capture: Discovery, Development, and Mechanism.
Yousefi, Roozbeh; Struble, Thomas J.; Payne, Jenna L.; Vishe, Mahesh; Schley, Nathan D.; Johnston, Jeffrey N.; Journal of the American Chemical Society 141 (2019) 618–625; doi:10.1021/jacs.8b11793

data_4133618
_publ_section_title
;
 Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl
 Amines by CO<sub>2</sub>-Capture: Discovery, Development, and Mechanism.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              618
_journal_page_last               625
_journal_paper_doi               10.1021/jacs.8b11793
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         '3(C H2 Cl2), C42 H44 N6 O2'
_chemical_formula_sum            'C45 H50 Cl6 N6 O2'
_chemical_formula_weight         919.61
_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             2018-03-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.5500(3)
_cell_length_b                   24.8696(5)
_cell_length_c                   25.0479(5)
_cell_measurement_reflns_used    16194
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.0710
_cell_measurement_theta_min      2.4860
_cell_volume                     9063.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1506
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -108.00 -35.00   1.00    6.00    --  -35.95-178.00-120.00   73
  2  \f      0.00 120.00   1.00    6.00 -40.00 -35.95   0.00    --   120
  3  \w     55.00 109.00   1.00    6.00    --   35.95-178.00  30.00   54
  4  \w     57.00 108.00   1.00    6.00    --   35.95 178.00 -30.00   51
  5  \w     82.00 167.00   1.00   30.00    --  100.36  61.00 -90.00   85
  6  \f    120.00 237.00   1.00   30.00 100.36 100.36  20.00    --   117
  7  \w     82.00 167.00   1.00   30.00    --  100.36  61.00-150.00   85
  8  \w    100.00 170.00   1.00   30.00    --  100.36 111.00 150.00   70
  9  \w     33.00 118.00   1.00   30.00    --  100.36 -61.00-120.00   85
 10  \w    100.00 170.00   1.00   30.00    --  100.36 111.00 -90.00   70
 11  \w     31.00 109.00   1.00   30.00    --  100.36 -94.00 120.00   78
 12  \w     30.00 122.00   1.00   30.00    --  100.36 -30.00-120.00   92
 13  \w   -103.00 -19.00   1.00    6.00    --  -35.95 -57.00 -90.00   84
 14  \w     57.00  97.00   1.00    6.00    --   35.95 178.00-150.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0615116000
_diffrn_orient_matrix_UB_12      0.0494785000
_diffrn_orient_matrix_UB_13      -0.0095858000
_diffrn_orient_matrix_UB_21      -0.0254880000
_diffrn_orient_matrix_UB_22      0.0217683000
_diffrn_orient_matrix_UB_23      0.0556722000
_diffrn_orient_matrix_UB_31      0.0823404000
_diffrn_orient_matrix_UB_32      -0.0302409000
_diffrn_orient_matrix_UB_33      0.0243198000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            44220
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        63.674
_diffrn_reflns_theta_max         63.674
_diffrn_reflns_theta_min         2.504
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.810
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.413
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.348
_exptl_crystal_description       block
_exptl_crystal_F_000             3840
_exptl_crystal_size_max          0.333
_exptl_crystal_size_mid          0.271
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.109
_refine_diff_density_min         -0.944
_refine_diff_density_rms         0.166
_refine_ls_abs_structure_details
;
 Flack x determined using 5196 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1067
_refine_ls_number_reflns         14841
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0908
_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^)+(0.1970P)^2^+4.4020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2480
_refine_ls_wR_factor_ref         0.2570
_reflns_Friedel_coverage         0.824
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                13342
_reflns_number_total             14841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11793_si_004.cif
_cod_data_source_block           7c
_cod_original_cell_volume        9063.7(3)
_cod_database_code               4133618
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C45H51Cl6N6O2
_shelx_estimated_absorpt_t_max   0.599
_shelx_estimated_absorpt_t_min   0.364
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C15B(H15B), C16B(H16B)
2.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C1G(H1GA,H1GB), C1F(H1FA,H1FB), C1C(H1CA,H1CB), C1D(H1DA,
 H1DB), C1E(H1EA,H1EB), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
  C11B(H11C,H11D), C12B(H12C,H12D), C13B(H13C,H13D), C14B(H14C,H14D), C39B(H39C,
 H39D), C40B(H40C,H40D), C41B(H41C,H41D), C42B(H42C,H42D)
2.c Aromatic/amide H refined with riding coordinates:
 N3(H3), N4(H4), C2(H2), C6(H6), C8(H8), C9(H9), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30),
  C34(H34), C36(H36), C37(H37), N3B(H3B), N4B(H4B), C2B(H2B), C6B(H6B),
 C8B(H8B), C9B(H9B), C18B(H18B), C19B(H19B), C20B(H20B), C21B(H21B), C22B(H22B),
  C24B(H24B), C25B(H25B), C26B(H26B), C27B(H27B), C28B(H28B), C30B(H30B),
 C34B(H34B), C36B(H36B), C37B(H37B)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C38(H38A,H38B,H38C), C10B(H10D,H10E,H10F), C38B(H38D,
 H38E,H38F)
;
_shelx_res_checksum              1123
_shelx_hkl_checksum              1779
_olex2_date_sample_data_collection 2018-03-14
_olex2_exptl_crystal_mounting_method 'mounted in a polyimide loop'
_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 1.250
_oxdiff_exptl_absorpt_empirical_full_min 0.820