Diversity-Oriented Synthesis of Heterocycles and Macrocycles by Controlled Reactions of Oxetanes with α-Iminocarbenes
Guarnieri-Ibáñez, Alejandro; Medina, Florian; Besnard, Céline; Kidd, Sarah L.; Spring, David R.; Lacour, Jerome; Chem. Sci.  (2017) –; doi:10.1039/C7SC00964J

data_1546300
_publ_section_title
;
 Diversity-Oriented Synthesis of Heterocycles and Macrocycles by
 Controlled Reactions of Oxetanes with \a-Iminocarbenes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC00964J
_journal_year                    2017
_chemical_formula_moiety         'C21 H25 N O3 S'
_chemical_formula_sum            'C21 H25 N O3 S'
_chemical_formula_weight         371.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2017-02-27 deposited with the CCDC.
2017-06-07 downloaded from the CCDC.
;
_cell_angle_alpha                117.600(6)
_cell_angle_beta                 110.658(5)
_cell_angle_gamma                94.009(4)
_cell_formula_units_Z            2
_cell_length_a                   10.6084(6)
_cell_length_b                   10.7200(5)
_cell_length_c                   10.8762(7)
_cell_measurement_reflns_used    6022
_cell_measurement_temperature    179(2)
_cell_measurement_theta_max      72.8360
_cell_measurement_theta_min      4.6150
_cell_volume                     984.19(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9825
_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    135.00 161.00   1.00    7.50    --  109.75  61.00 -60.00   26
  2  \w    117.00 178.00   1.00    7.50    --  109.75  77.00-150.00   61
  3  \w    116.00 144.00   1.00    2.00    --   60.00  77.00-118.63   28
  4  \w     98.00 139.00   1.00    2.00    --   60.00  69.00 -50.26   41
  5  \w    102.00 151.00   1.00    2.00    --   68.00  75.00 -21.05   49
  6  \w    109.00 135.00   1.00    7.50    --  109.75  77.00-120.00   26
  7  \w     82.00 172.00   1.00    7.50    --  109.75  61.00 -90.00   90
  8  \w     74.00 176.00   1.00    7.50    --  109.75  77.00-180.00  102
  9  \w     79.00 125.00   1.00    7.50    --  109.75  61.00 -60.00   46
 10  \w     79.00 107.00   1.00    7.50    --  109.75  61.00-120.00   28
 11  \w     74.00 100.00   1.00    7.50    --  109.75  77.00 -90.00   26
 12  \w     74.00 100.00   1.00    7.50    --  109.75  77.00-120.00   26
 13  \w     74.00 100.00   1.00    7.50    --  109.75  77.00-150.00   26
 14  \w     68.00 151.00   1.00    2.00    --   68.00  76.00-151.04   83
 15  \w     77.00 153.00   1.00    7.50    --  109.75  61.00   0.00   76
 16  \w    113.00 177.00   1.00    7.50    --  109.75  77.00 120.00   64
 17  \w    113.00 145.00   1.00    7.50    --  109.75  77.00 150.00   32
 18  \w     94.00 127.00   1.00    2.00    --   64.00  76.00 179.27   33
 19  \w     78.00 108.00   1.00    7.50    --  109.75  61.00 150.00   30
 20  \w     74.00  99.00   1.00    7.50    --  109.75  77.00 120.00   25
 21  \w     74.00 148.00   1.00    7.50    --  109.75  77.00  90.00   74
 22  \w     78.00 103.00   1.00    7.50    --  109.75  61.00  60.00   25
 23  \w     75.00 177.00   1.00    7.50    --  109.75  77.00  60.00  102
 24  \w     74.00 174.00   1.00    7.50    --  109.75  77.00  30.00  100
 25  \w     77.00 108.00   1.00    7.50    --  109.75  77.00 150.00   31
 26  \w     49.00  81.00   1.00    7.50    --   84.00  66.00  47.84   32
 27  \w     77.00 103.00   1.00    7.50    --  109.75  61.00  30.00   26
 28  \w     77.00 178.00   1.00    7.50    --  109.75  61.00 -30.00  101
 29  \w     74.00 100.00   1.00    7.50    --  109.75  77.00 -30.00   26
 30  \w     34.00  64.00   1.00    2.00    --   68.00  76.00-151.04   30
 31  \w     27.00  66.00   1.00    2.00    --   60.00  77.00-118.63   39
 32  \w     25.00  56.00   1.00    2.00    --   60.00  69.00 -50.26   31
 33  \w     32.00  75.00   1.00    2.00    --   68.00  75.00 -21.05   43
 34  \w     26.00  55.00   1.00    2.00    --   60.00  76.00  32.62   29
 35  \w     20.00  45.00   1.00    2.00    --   56.00  79.00 106.09   25
 36  \w     29.00  71.00   1.00    2.00    --   64.00  73.00 117.96   42
 37  \w     28.00  54.00   1.00    2.00    --   64.00  76.00 179.27   26
 38  \w     10.00  35.00   1.00    2.00    --   48.00  85.00 179.26   25
 39  \w     19.00  44.00   1.00    2.00    --   56.00  80.00  75.49   25
 40  \w      3.00  28.00   1.00    2.00    --   44.00  90.00  -8.62   25
 41  \w     20.00  45.00   1.00    2.00    --   56.00  79.00 -53.90   25
 42  \w    -52.00  -8.00   1.00    2.00    --  -38.94 -57.00 -60.00   44
 43  \w    -28.00  -3.00   1.00    2.00    --  -38.94 -77.00-180.00   25
 44  \w     27.00  90.00   1.00    2.00    --   38.94-125.00-180.00   63
 45  \w     33.00  87.00   1.00    7.50    --  109.75 -94.00-180.00   54
 46  \w     23.00 108.00   1.00    7.50    --  109.75 -94.00-120.00   85
 47  \w     34.00  95.00   1.00    7.50    --  109.75 -94.00 -30.00   61
 48  \w     23.00  89.00   1.00    2.00    --   38.94-125.00  30.00   66
 49  \w     27.00 109.00   1.00    7.50    --  109.75 -94.00  30.00   82
 50  \w     28.00 116.00   1.00    7.50    --  109.75-111.00 150.00   88
 51  \w    -71.00  21.00   1.00    2.00    --  -38.94  57.00 -60.00   92
 52  \w    -87.00 -10.00   1.00    2.00    --  -38.94 -38.00  30.00   77
 53  \w   -117.00 -59.00   1.00    2.00    --  -38.94 -57.00 -60.00   58
 54  \w   -123.00 -37.00   1.00    2.00    --  -38.94 -77.00-180.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1553819000
_diffrn_orient_matrix_UB_12      0.0038031000
_diffrn_orient_matrix_UB_13      0.0408200000
_diffrn_orient_matrix_UB_21      -0.0442607000
_diffrn_orient_matrix_UB_22      -0.1658548000
_diffrn_orient_matrix_UB_23      -0.1181244000
_diffrn_orient_matrix_UB_31      -0.0074714000
_diffrn_orient_matrix_UB_32      0.0321799000
_diffrn_orient_matrix_UB_33      -0.1261480000
_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  0.0391
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            14460
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.301
_diffrn_reflns_theta_min         4.642
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.617
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.692
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.493
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.407
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         3882
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0661P)^2^+0.1858P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1124
_refine_ls_wR_factor_ref         0.1187
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3343
_reflns_number_total             3882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc00964j2.cif
_cod_data_source_block           ajgi268-2-1
_cod_original_cell_volume        984.19(11)
_cod_database_code               1546300
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C21-C20 = C23-C21 = C24-C21 = C22-C21 = C22-C18
 1.55 with sigma of 0.02
 C22B-C21B = C22B-C18B = C21B-C20B = C24-C21B = C23B-C21B
 1.55 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O19B) = Uanis(C22)
Uanis(C22B) = Uanis(O19)
Uanis(C18) = Uanis(C18B)
Uanis(C21) = Uanis(C21B)
4. Rigid body (RIGU) restrains
 C16, C17, C21B, C22B, O19B, C20B, C23B, C18B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O19, C18, C21B, C20, C23, C24, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H17C)=Sof(H17D)=Sof(C21B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C22B)=
 Sof(H22C)=Sof(H22D)=Sof(O19B)=Sof(C20B)=Sof(H20C)=Sof(H20D)=Sof(C23B)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C18B)=1-FVAR(1)
 Sof(O19)=Sof(C18)=Sof(H17A)=Sof(H17B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C23)=
 Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C22)=Sof(H22A)=
 Sof(H22B)=Sof(C21)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B), C17(H17C,H17D), C20(H20A,H20B), C22(H22A,
 H22B), C22B(H22C,H22D), C20B(H20C,H20D)
6.b Me refined with riding coordinates:
 C24(H24D,H24E,H24F), C24(H24A,H24B,H24C)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C12(H12), C8(H8), C15(H15), C13(H13), C14(H14), C7(H7), C5(H5)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C0AA(H0AA,H0AB,H0AC), C23B(H23D,H23E,H23F)
;
_shelx_shelxl_version_number     2016/6
_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 2.568
_oxdiff_exptl_absorpt_empirical_full_min 0.424