Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria
Mikan, Charles P.; Matthews, Aidan; Harris, Daniel; McIvor, Charlotte E.; Waddell, Paul G.; Sims, Mark T.; Knowles, Jonathan P.; Chemical Science 14 (2023) 6992–6996; doi:10.1039/D3SC02303F

data_1569348
_publ_section_title
;
 Stereoselective two-carbon ring expansion of allylic amines via
 electronic control of palladium-promoted equilibria
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              6992
_journal_page_last               6996
_journal_paper_doi               10.1039/D3SC02303F
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H25 N O2'
_chemical_formula_sum            'C22 H25 N O2'
_chemical_formula_weight         335.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-20 deposited with the CCDC.	2023-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.912(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.9158(3)
_cell_length_b                   7.5748(3)
_cell_length_c                   17.5449(6)
_cell_measurement_reflns_used    7072
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      76.8560
_cell_measurement_theta_min      5.0290
_cell_volume                     915.73(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.60a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.930
_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    -82.00 -45.00   0.50    0.30    --  -92.45  77.00-150.00   74
  2  \w    -68.00 -23.00   0.50    0.30    --  -92.45  61.00-150.00   90
  3  \w    -33.00  -8.00   0.50    0.30    --  -92.45  30.00-120.00   50
  4  \w    -35.00 -10.00   0.50    0.30    --  -92.45  30.00-180.00   50
  5  \w    -24.00  36.00   0.50    0.30    --  -47.19  19.00-180.00  120
  6  \w     45.00  83.00   0.50    0.30    --  108.17 -95.00  90.00   76
  7  \w     34.00 103.00   0.50    0.30    --  108.17 -95.00 120.00  138
  8  \w     17.00  43.00   0.50    0.30    --   54.00  87.00 149.98   52
  9  \w      8.00  33.00   0.50    0.30    --   50.00  92.00 126.38   50
 10  \w     37.00  63.00   0.50    0.30    --   70.00  77.00 178.16   52
 11  \w     76.00 101.00   0.50    0.30    --   97.31  77.00 120.00   50
 12  \w    106.00 131.00   0.50    0.30    --   70.00  77.00 178.16   50
 13  \w    102.00 136.00   0.50    0.30    --  108.17  19.00  74.00   68
 14  \w     79.00 104.00   0.50    0.30    --   97.31  19.00  74.00   50
 15  \w     52.00  78.00   0.50    0.30    --  108.17  19.00  74.00   52
 16  \w     38.00  68.00   0.50    0.30    --   70.00  77.00-149.67   60
 17  \w      7.00  32.00   0.50    0.30    --   50.00  93.00-166.57   50
 18  \w    152.00 178.00   0.50    0.30    --  108.17  19.00  74.00   52
 19  \w     87.00 123.00   0.50    0.30    --   46.19  19.00  74.00   72
 20  \w     64.00  92.00   0.50    0.30    --   46.19  38.00 120.00   56
 21  \w     20.00  59.00   0.50    0.30    --   46.19  38.00 120.00   78
 22  \w    -20.00  18.00   0.50    0.30    --   46.19  19.00  74.00   76
 23  \w     21.00  78.00   0.50    0.30    --   46.19  19.00  74.00  114
 24  \w     20.00  71.00   0.50    0.30    --   97.31 -61.00  60.00  102
 25  \w     21.00  70.00   0.50    0.30    --   97.31 -61.00 120.00   98
 26  \w     20.00  67.00   0.50    0.30    --   97.31 -61.00 -30.00   94
 27  \w    -33.00  -7.00   0.50    0.30    --   46.19 -19.00 -92.00   52
 28  \w    -98.00 -45.00   0.50    0.30    --  -78.00 -77.00  98.74  106
 29  \w    -89.00 -61.00   0.50    0.30    --  -92.45 -77.00 120.00   56
 30  \w   -163.00 -62.00   0.50    0.30    --  -92.45 -77.00 150.00  202
 31  \w   -156.00-109.00   0.50    0.30    --  -92.45 -77.00 120.00   94
 32  \w    -90.00 -62.00   0.50    0.30    --  -92.45 -77.00-120.00   56
 33  \w   -164.00 -96.00   0.50    0.30    --  -92.45 -77.00-120.00  136
 34  \w   -155.00 -63.00   0.50    0.30    --  -92.45 -77.00-180.00  184
 35  \w    -84.00 -59.00   0.50    0.30    --  -92.45 -77.00-150.00   50
 36  \w   -132.00 -64.00   0.50    0.30    --  -94.00 -70.00-145.72  136
 37  \w   -164.00-139.00   0.50    0.30    --  -94.00 -70.00-145.72   50
 38  \w    -79.00 -54.00   0.50    0.30    --  -47.19 -19.00 -92.00   50
 39  \w   -124.00 -99.00   0.50    0.30    --  -92.45 -19.00 -92.00   50
 40  \w   -160.00 -86.00   0.50    0.30    --  -92.45 -61.00  90.00  148
 41  \w    -86.00 -60.00   0.50    0.30    --  -78.00 -72.00 125.20   52
 42  \w    -94.00 -60.00   0.50    0.30    --  -82.00 -68.00 176.12   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1951175000
_diffrn_orient_matrix_UB_12      0.0496357000
_diffrn_orient_matrix_UB_13      -0.0437658000
_diffrn_orient_matrix_UB_21      0.0956516000
_diffrn_orient_matrix_UB_22      -0.0071883000
_diffrn_orient_matrix_UB_23      -0.0760074000
_diffrn_orient_matrix_UB_31      -0.0525834000
_diffrn_orient_matrix_UB_32      -0.1971519000
_diffrn_orient_matrix_UB_33      -0.0085652000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            10179
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.942
_diffrn_reflns_theta_min         5.060
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.606
_exptl_absorpt_correction_T_max  0.973
_exptl_absorpt_correction_T_min  0.907
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.60a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             360
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.194
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1350 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_coef       0.0042(15)
_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   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3474
_refine_ls_number_restraints     187
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0671P)^2^+0.2566P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.800
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.871
_reflns_number_gt                3264
_reflns_number_total             3474
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02303f2.cif
_cod_data_source_block           jkpw001_lt_fa
_cod_database_code               1569348
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C22 H25 N1 O3'
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.863
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C16(H16A,H16B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22)
3.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              56837
_shelx_hkl_checksum              37634
_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 1.330
_oxdiff_exptl_absorpt_empirical_full_min 0.669