Decarboxylative Amination: Diazirines as Single and Double Electrophilic Nitrogen Transfer Reagents.
Chandrachud, Preeti P.; Wojtas, Lukasz; Lopchuk, Justin M.; Journal of the American Chemical Society 142 (2020) 21743–21750; doi:10.1021/jacs.0c09403

data_4135413
_publ_section_title
;
 Decarboxylative Amination: Diazirines as Single and Double Electrophilic
 Nitrogen Transfer Reagents.
;
_journal_issue                   52
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              21743
_journal_page_last               21750
_journal_paper_doi               10.1021/jacs.0c09403
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety
'1(C13 H15 F3 N2 O2 S), 0.14(C H2 Cl2), 0.14(C6 H14), 0.08(Cl)'
_chemical_formula_sum            'C13.99 H17.25 Cl0.35 F3 N2 O2 S'
_chemical_formula_weight         346.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.6560(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.4287(3)
_cell_length_b                   14.0260(5)
_cell_length_c                   25.9572(9)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.77
_cell_measurement_theta_min      3.44
_cell_volume                     3393.7(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON II CPAD'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            43734
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         80.298
_diffrn_reflns_theta_min         3.444
_diffrn_source                   'INCOATEC Imus micro-focus source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.563
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6752
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1242 before and 0.0796 after correction.
The Ratio of minimum to maximum transmission is 0.6752.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       needle
_exptl_crystal_F_000             1441
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.556
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     847
_refine_ls_number_reflns         7101
_refine_ls_number_restraints     966
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0553
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0791P)^2^+2.8954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1533
_refine_ls_wR_factor_ref         0.1622
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5956
_reflns_number_total             7101
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09403_si_003.cif
_cod_data_source_block           B
_cod_depositor_comments
'Adding full bibliography for 4135411--4135418.cif.'
_cod_database_code               4135413
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.555
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H21C,H21D,H12B} of C21B, {H51C,H51D,H42B} of C51B, All
  C(H,H) groups
 At 1.5 times of:
  {H71A,H71B,H71C} of C71, {H76A,H76B,H76C} of C76
2. Restrained distances
 C76-C75 = C75-C74 = C74-C73 = C73-C72 = C72-C71
 1.49 with sigma of 0.02
 Cl63-C61 = Cl62-C61 = Cl82-C81 = Cl83-C81
 1.75 with sigma of 0.01
 C71-C73 = C72-C74 = C73-C75 = C74-C76
 2.5 with sigma of 0.04
 Cl63-Cl62 = Cl82-Cl83
 2.9 with sigma of 0.02
 C7B-H12B \\sim H12B-N13B
 with sigma of 0.02
 C37B-H42B \\sim H42B-N43B
 with sigma of 0.02
 N42A-H42A \\sim N12A-H12A \\sim N42B-H42B \\sim N12B-H12B
 with sigma of 0.02
3. Restrained planarity
 C71, C72, C73, C74, C75, C76
 with sigma of 0.1
 C6B, C5B, C4B, C3B, C2B, C1B
 with sigma of 0.001
 C36B, C35B, C34B, C33B, C32B, C31B
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
C7B \\sim C1B \\sim C2B \\sim C6B \\sim C3B \\sim C5B \\sim C4B \\sim C8B \\sim
N12B \\sim N13B \\sim F9B \\sim F10B \\sim F11B \\sim C14B \\sim C15B \\sim
C21B \\sim C16B \\sim C20B \\sim S17B \\sim O18B \\sim O19B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Cl62 \\sim Cl63 \\sim C61 \\sim Cl86 \\sim C71 \\sim C72 \\sim C73 \\sim C74
\\sim C75 \\sim C76 \\sim Cl82 \\sim C81 \\sim Cl83 \\sim Cl85 \\sim C5B \\sim
C4B \\sim C3B \\sim F9B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C33B \\sim C31B \\sim C32B \\sim C36B \\sim C35B \\sim C37B \\sim C34B \\sim
C38B \\sim N42B \\sim N43B \\sim F39B \\sim F40B \\sim F41B \\sim C44B \\sim
C45B \\sim C51B \\sim C46B \\sim C50B \\sim S47B \\sim O48B \\sim O49B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C36B \\sim C35B \\sim C34B \\sim C33B \\sim C32B \\sim C31B \\sim C37B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15B) \\sim Ueq: with sigma of 0.00625 and sigma for terminal atoms of
0.0125
Uanis(O49B) = Uanis(C44A)
5. Rigid body (RIGU) restrains
 C7B, C1B, C2B, C6B, C3B, C5B, C4B, C8B, N12B, N13B, F9B, F10B, F11B, C14B,
 C15B, C21B, C16B, C20B, S17B, O18B, O19B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33B, C31B, C32B, C36B, C35B, C37B, C34B, C38B, N42B, N43B, F39B, F40B, F41B,
 C44B, C45B, C51B, C46B, C50B, S47B, O48B, O49B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, F9A, F10A, F11A, N12A, N13A, C14A,
C15A, C16A, S17A, O18A, O19A, C20A, C21A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, F9B, F10B, F11B, N12B, N13B, C14B,
C15B, C16B, S17B, O18B, O19B, C20B, C21B}
{C31A, C32A, C33A, C34A, C35A, C36A, C37A, C38A, F39A, F40A, F41A, N42A, N43A,
C44A, C45A, C46A, S47A, O48A, O49A, C50A, C51A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C31B, C32B, C33B, C34B, C35B, C36B, C37B, C38B, F39B, F40B, F41B, N42B, N43B,
C44B, C45B, C46B, S47B, O48B, O49B, C50B, C51B}
7. Others
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(C8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=
 Sof(N12B)=Sof(N13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15C)=Sof(H15D)=
 Sof(C16B)=Sof(H16C)=Sof(H16D)=Sof(S17B)=Sof(O18B)=Sof(O19B)=Sof(C20B)=
 Sof(H20C)=Sof(H20D)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(H12B)=Sof(C31B)=
 Sof(H31B)=Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=
 Sof(C35B)=Sof(H35B)=Sof(C36B)=Sof(C37B)=Sof(C38B)=Sof(F39B)=Sof(F40B)=
 Sof(F41B)=Sof(N42B)=Sof(N43B)=Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45C)=
 Sof(H45D)=Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(S47B)=Sof(O48B)=Sof(O49B)=
 Sof(C50B)=Sof(H50C)=Sof(H50D)=Sof(C51B)=Sof(H51C)=Sof(H51D)=Sof(H42B)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=
 Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=
 Sof(N12A)=Sof(H12A)=Sof(N13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=
 Sof(H15B)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(S17A)=Sof(O18A)=Sof(O19A)=
 Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=
 Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(C37A)=Sof(C38A)=Sof(F39A)=Sof(F40A)=
 Sof(F41A)=Sof(N42A)=Sof(H42A)=Sof(N43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=
 Sof(H45A)=Sof(H45B)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(S47A)=Sof(O48A)=
 Sof(O49A)=Sof(C50A)=Sof(H50A)=Sof(H50B)=Sof(C51A)=Sof(H51A)=Sof(H51B)=FVAR(1)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(Cl62)=Sof(Cl63)=FVAR(2)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(Cl82)=Sof(Cl83)=FVAR(3)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=
 Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(4)
8.a Ternary CH refined with riding coordinates:
 C14A(H14A), C44A(H44A), C14B(H14B), C44B(H44B)
8.b Secondary CH2 refined with riding coordinates:
 C15A(H15A,H15B), C16A(H16A,H16B), C20A(H20A,H20B), C21A(H21A,H21B), C45A(H45A,
 H45B), C46A(H46A,H46B), C50A(H50A,H50B), C51A(H51A,H51B), C15B(H15C,H15D),
 C16B(H16C,H16D), C20B(H20C,H20D), C21B(H21C,H21D), C45B(H45C,H45D), C46B(H46C,
 H46D), C50B(H50C,H50D), C51B(H51C,H51D), C61(H61A,H61B), C81(H81A,H81B),
 C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B)
8.c Me refined with riding coordinates:
 C71(H71A,H71B,H71C), C76(H76A,H76B,H76C)
8.d Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C31A(H31A), C32A(H32A),
 C33A(H33A), C34A(H34A), C35A(H35A), C1B(H1B), C2B(H2B), C3B(H3B), C4B(H4B),
 C5B(H5B), C31B(H31B), C32B(H32B), C33B(H33B), C34B(H34B), C35B(H35B)
;
_shelx_res_checksum              86446
_shelx_hkl_checksum              23632
_olex2_submission_special_instructions 'No special instructions were received'