Regiodivergent (3 + 2) annulation reactions of oxyallyl cations.
Protich, Zachary; Lowder, Leah L.; Hughes, Russell P.; Wu, Jimmy; Chemical science 14 (2023) 5196–5203; doi:10.1039/d2sc06999g

data_1568954
_publ_section_title
;
 Regiodivergent (3 + 2) annulation reactions of oxyallyl cations.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              5196
_journal_page_last               5203
_journal_paper_doi               10.1039/d2sc06999g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C16 H19 N O'
_chemical_formula_sum            'C16 H19 N O'
_chemical_formula_weight         241.32
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2022-09-23
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-21 deposited with the CCDC.	2023-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.1247(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.04898(14)
_cell_length_b                   6.21142(6)
_cell_length_c                   15.50317(18)
_cell_measurement_reflns_used    19091
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7910
_cell_measurement_theta_min      3.2560
_cell_volume                     1299.65(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (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, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -60.00 -27.00   0.50    0.05    --  -47.44  57.00 120.00   66
  2  \w    -22.00  11.00   0.50    0.05    --  -47.44  57.00 120.00   66
  3  \w    -13.00  14.00   0.50    0.05    --  -47.44  57.00  30.00   54
  4  \w    -21.00  23.00   0.50    0.05    --  -47.44  39.00  15.00   88
  5  \w    -62.00 -26.00   0.50    0.05    --  -47.44  57.00  30.00   72
  6  \w    -70.00  -6.00   0.50    0.05    --  -47.44  77.00-120.00  128
  7  \w     35.00  91.00   0.50    0.05    --   47.44  39.00  15.00  112
  8  \w     38.00  64.00   0.50    0.05    --   47.44  31.00 -13.03   52
  9  \w     37.00  62.00   0.50    0.05    --   47.44  31.00 -74.01   50
 10  \w     37.00  63.00   0.50    0.05    --   47.44  30.00 -86.78   52
 11  \w     36.00  93.00   0.50    0.05    --   47.44  30.00-143.06  114
 12  \w     35.00  60.00   0.50    0.05    --   47.44  31.00  65.58   50
 13  \w     35.00  60.00   0.50    0.05    --   47.44  31.00 116.49   50
 14  \w     38.00  64.00   0.50    0.05    --   47.44  31.00 148.10   52
 15  \w    140.00 165.00   0.50    0.05    --  113.25  77.00 150.00   50
 16  \w    137.00 162.00   0.50    0.05    --  113.25  30.00 120.00   50
 17  \w    140.00 165.00   0.50    0.05    --  113.25  61.00  30.00   50
 18  \w    102.00 168.00   0.50    0.05    --  113.25  30.00  90.00  132
 19  \w    101.00 132.00   0.50    0.05    --  113.25  30.00 120.00   62
 20  \w    101.00 176.00   0.50    0.05    --  113.25  39.00  15.00  150
 21  \w    102.00 127.00   0.50    0.05    --  113.25  30.00 -60.00   50
 22  \w    143.00 178.00   0.50    0.05    --  113.25  30.00 -60.00   70
 23  \w    143.00 173.00   0.50    0.05    --  113.25  61.00-180.00   60
 24  \w    141.00 178.00   0.50    0.05    --  113.25  30.00-150.00   74
 25  \w    101.00 132.00   0.50    0.05    --  113.25  30.00-150.00   62
 26  \w    107.00 169.00   0.50    0.05    --  113.25  30.00-180.00  124
 27  \w    130.00 176.00   0.50    0.05    --  113.25  77.00 -90.00   92
 28  \w    138.00 172.00   0.50    0.05    --  113.25  30.00-120.00   68
 29  \w    101.00 178.00   0.50    0.05    --  113.25  30.00   0.00  154
 30  \w    132.00 177.00   0.50    0.05    --  113.25  30.00  30.00   90
 31  \w    151.00 176.00   0.50    0.05    --  113.25  30.00  60.00   50
 32  \w    102.00 162.00   0.50    0.05    --  113.25  30.00 150.00  120
 33  \w    105.00 133.00   0.50    0.05    --  113.25  30.00  60.00   56
 34  \w    101.00 136.00   0.50    0.05    --  113.25  22.00 -27.80   70
 35  \w    144.00 175.00   0.50    0.05    --  113.25  22.00 -27.80   62
 36  \w    144.00 170.00   0.50    0.05    --  113.25  30.00 -90.00   52
 37  \w    103.00 129.00   0.50    0.05    --  113.25  30.00-120.00   52
 38  \w    103.00 129.00   0.50    0.05    --  113.25  30.00 -90.00   52
 39  \w    109.00 163.00   0.50    0.05    --  113.25 125.00-150.00  108
 40  \w     75.00 101.00   0.50    0.05    --  113.25 -77.00 150.00   52
 41  \w     42.00  70.00   0.50    0.05    --  113.25 -77.00 150.00   56
 42  \w     43.00  69.00   0.50    0.05    --  113.25 -61.00 150.00   52
 43  \w     43.00  69.00   0.50    0.05    --  113.25 -61.00   0.00   52
 44  \w     43.00  70.00   0.50    0.05    --  113.25 -61.00  30.00   54
 45  \w     45.00  70.00   0.50    0.05    --  113.25 -61.00 -60.00   50
 46  \w     44.00  70.00   0.50    0.05    --  113.25 -61.00-120.00   52
 47  \w     42.00  68.00   0.50    0.05    --  113.25 -61.00-150.00   52
 48  \w    -15.00  40.00   0.50    0.05    --   47.44 -39.00-138.00  110
 49  \w     45.00 108.00   0.50    0.05    --  113.25-125.00  30.00  126
 50  \w     51.00 104.00   0.50    0.05    --  113.25 -94.00  60.00  106
 51  \w     44.00 108.00   0.50    0.05    --  113.25-125.00   0.00  128
 52  \w     82.00 108.00   0.50    0.05    --  113.25-125.00 -30.00   52
 53  \w     45.00  77.00   0.50    0.05    --  113.25-125.00 -30.00   64
 54  \w     42.00 102.00   0.50    0.05    --  113.25 -94.00-120.00  120
 55  \w     44.00  70.00   0.50    0.05    --  113.25 -94.00 120.00   52
 56  \w     42.00 102.00   0.50    0.05    --  113.25 -94.00 150.00  120
 57  \w     79.00 104.00   0.50    0.05    --  113.25 -94.00  90.00   50
 58  \w     74.00 100.00   0.50    0.05    --  113.25 -94.00 120.00   52
 59  \w     48.00  74.00   0.50    0.05    --  113.25 -94.00  90.00   52
 60  \w     48.00 104.00   0.50    0.05    --  113.25 -94.00  30.00  112
 61  \w     76.00 101.00   0.50    0.05    --  113.25 -94.00-150.00   50
 62  \w     42.00  71.00   0.50    0.05    --  113.25 -94.00-150.00   58
 63  \w    -61.00 -36.00   0.50    0.05    --  -47.44 -28.00  95.48   50
 64  \w   -121.00 -40.00   0.50    0.05    --  -47.44 -30.00  -1.73  162
 65  \w   -120.00 -34.00   0.50    0.05    --  -47.44 -39.00-138.00  172
 66  \w    -64.00 -39.00   0.50    0.05    --  -47.44 -31.00-120.99   50
 67  \w   -119.00 -75.00   0.50    0.05    --  -47.44 -29.00 -50.34   88
 68  \w    -60.00 -35.00   0.50    0.05    --  -47.44 -29.00 -50.34   50
 69  \w    -45.00 -19.00   0.50    0.05    --  -91.75  39.00  15.00   52
 70  \w    -82.00 -41.00   0.50    0.05    --  -47.44 -30.00  74.21   82
 71  \w   -114.00 -85.00   0.50    0.05    --  -47.44 -30.00  74.21   58
 72  \w   -103.00 -78.00   0.50    0.05    --  -91.75 -25.00  -2.46   50
 73  \w   -114.00 -88.00   0.50    0.05    --  -91.75 -30.00  90.00   52
 74  \w   -116.00 -90.00   0.50    0.05    --  -91.75 -30.00  43.10   52
 75  \w   -114.00 -88.00   0.50    0.05    --  -91.75 -30.00 -69.91   52
 76  \w   -110.00 -78.00   0.50    0.05    --  -91.75 -39.00-138.00   64
 77  \w   -110.00 -82.00   0.50    0.05    --  -91.75 -29.00 -51.31   56
 78  \w   -152.00-126.00   0.50    0.05    --  -91.75 -30.00 -69.91   52
 79  \w   -155.00-129.00   0.50    0.05    --  -91.75 -29.00 -15.51   52
 80  \w   -106.00 -79.00   0.50    0.05    --  -91.75 -29.00 141.30   54
 81  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -29.00 165.25   50
 82  \w   -156.00-130.00   0.50    0.05    --  -91.75 -29.00 141.30   52
 83  \w   -162.00-136.00   0.50    0.05    --  -91.75 -29.00 165.25   52
 84  \w   -106.00 -79.00   0.50    0.05    --  -91.75 -29.00 104.51   54
 85  \w   -104.00 -79.00   0.50    0.05    --  -91.75 -27.00 112.80   50
 86  \w   -105.00 -79.00   0.50    0.05    --  -91.75 -29.00  54.77   52
 87  \w   -165.00-139.00   0.50    0.05    --  -91.75 -27.00 112.80   52
 88  \w   -107.00 -82.00   0.50    0.05    --  -91.75 -29.00 -28.14   50
 89  \w   -106.00 -80.00   0.50    0.05    --  -91.75 -29.00 -15.51   52
 90  \w   -109.00 -83.00   0.50    0.05    --  -91.75 -26.00 -96.16   52
 91  \w   -111.00 -79.00   0.50    0.05    --  -91.75 -27.00-117.65   64
 92  \w   -106.00 -80.00   0.50    0.05    --  -91.75 -29.00-177.71   52
 93  \w   -152.00-110.00   0.50    0.05    --  -91.75-125.00   0.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1130773000
_diffrn_orient_matrix_UB_12      -0.0328097000
_diffrn_orient_matrix_UB_13      0.0243331000
_diffrn_orient_matrix_UB_21      -0.0157067000
_diffrn_orient_matrix_UB_22      -0.2233069000
_diffrn_orient_matrix_UB_23      -0.0450269000
_diffrn_orient_matrix_UB_31      0.0019822000
_diffrn_orient_matrix_UB_32      0.1029641000
_diffrn_orient_matrix_UB_33      -0.0898337000
_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  0.0323
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            28434
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.079
_diffrn_reflns_theta_min         3.760
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.584
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
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    1.233
_exptl_crystal_description       irregular
_exptl_crystal_F_000             520
_exptl_crystal_recrystallization_method 'used as receieved'
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.165
_refine_diff_density_max         0.304
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.0066(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     167
_refine_ls_number_reflns         2808
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0412P)^2^+0.5829P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0959
_refine_ls_wR_factor_ref         0.0967
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2690
_reflns_number_total             2808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06999g2.cif
_cod_data_source_block           jw922a
_cod_depositor_comments
'Adding full bibliography for 1568950--1568954.cif.'
_cod_database_code               1568954
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C15H17NO
_chemical_oxdiff_usercomment     ZTP-4-33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              32154
_shelx_hkl_checksum              91560
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id ZTP-4-33
_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 1.207
_oxdiff_exptl_absorpt_empirical_full_min 0.782