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_1569349
_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         'C10 H15 O4 S, C24 H30 N O4, H2 O, C H2 Cl2'
_chemical_formula_sum            'C35 H49 Cl2 N O9 S'
_chemical_formula_weight         730.71
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-11
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.14570(10)
_cell_length_b                   14.9447(3)
_cell_length_c                   33.7430(7)
_cell_measurement_reflns_used    6813
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      71.2040
_cell_measurement_theta_min      3.2160
_cell_volume                     3603.43(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (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_environment      N~2~
_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 0.932
_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   -123.00 -86.00   0.50    6.67    --  -49.76-128.00  76.00   74
  2  \w    -12.00  25.00   0.50    6.67    --  -49.76  13.00 -53.00   74
  3  \w   -160.00-134.00   0.50    6.67    --  -92.01-115.00 -21.00   52
  4  \w     71.00 111.00   0.50    6.67    --   96.11-128.00  76.00   80
  5  \w     34.00  59.00   0.50    6.67    --   96.11-128.00  76.00   50
  6  \w     -6.00  27.00   0.50    6.67    --   48.76 -19.00 -60.00   66
  7  \w    -29.00  37.00   0.50    6.67    --   48.76 -38.00  60.00  132
  8  \w    -15.00  11.00   0.50    6.67    --  -49.76  19.00-180.00   52
  9  \w    -49.00 -18.00   0.50    6.67    --  -92.01  45.00  30.00   62
 10  \w    -47.00 -15.00   0.50    6.67    --  -92.01  45.00  90.00   64
 11  \w    -46.00 -18.00   0.50    6.67    --  -92.01  45.00  60.00   56
 12  \w    -83.00 -31.00   0.50    6.67    --  -92.01 -13.00 134.00  104
 13  \w   -160.00 -95.00   0.50    6.67    --  -92.01 -13.00 134.00  130
 14  \w     18.00  49.00   0.50    6.67    --   96.11 -45.00 -90.00   62
 15  \w     18.00  43.00   0.50    6.67    --   96.11 -45.00 -60.00   50
 16  \w     25.00  50.00   0.50    6.67    --   96.11 -45.00-120.00   50
 17  \w     43.00  76.00   0.50    6.67    --  108.00 -95.00  30.00   66
 18  \w     40.00 105.00   0.50    6.67    --  108.00 -77.00  60.00  130
 19  \w     43.00  68.00   0.50    6.67    --  108.00 -61.00 120.00   50
;
_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      0.0289436000
_diffrn_orient_matrix_UB_12      0.0933605000
_diffrn_orient_matrix_UB_13      -0.0183307000
_diffrn_orient_matrix_UB_21      0.0243091000
_diffrn_orient_matrix_UB_22      0.0401817000
_diffrn_orient_matrix_UB_23      0.0417524000
_diffrn_orient_matrix_UB_31      0.2121984000
_diffrn_orient_matrix_UB_32      -0.0173227000
_diffrn_orient_matrix_UB_33      -0.0023156000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            18158
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.247
_diffrn_reflns_theta_min         2.619
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.613
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.692
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (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    1.347
_exptl_crystal_description       plate
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.494
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 2204 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.032(8)
_refine_ls_extinction_coef       0.00098(18)
_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   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         7049
_refine_ls_number_restraints     788
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0617
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0570P)^2^+2.3389P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1233
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.729
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.891
_reflns_number_gt                6175
_reflns_number_total             7049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02303f2.cif
_cod_data_source_block           jkpw003_fa
_cod_database_code               1569349
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C35 H49 Cl2 N1 O9 S1'
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.561
_reflns_odcompleteness_completeness 99.89
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 Cl1-C35 \\sim Cl3-C01D
 with sigma of 0.02
 Cl2-C35 \\sim Cl-C01D
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl3-Cl
 with sigma of 0.04
 C26-C33A \\sim C26-C33B
 with sigma of 0.04
 C26-C34A \\sim C26-C34B
 with sigma of 0.04
 C26-C30A \\sim C26-C30B
 with sigma of 0.04
 C32A-C28A \\sim C32B-C28B
 with sigma of 0.04
 O8-C27A \\sim O00I-C27B
 with sigma of 0.02
 C30A-C32A \\sim C30B-C32B
 with sigma of 0.04
 C26-C32A \\sim C26-C32B
 with sigma of 0.02
 C29A-C27A \\sim C29B-C27B
 with sigma of 0.04
 C26-C27A \\sim C26-C27B
 with sigma of 0.02
 C26-C31A \\sim C26-C31B
 with sigma of 0.02
 C34A-C33A \\sim C34B-C33B
 with sigma of 0.04
 C26-C29A \\sim C26-C29B
 with sigma of 0.04
 C30A-C29A \\sim C30B-C29B
 with sigma of 0.02
 C26-C28A \\sim C26-C28B
 with sigma of 0.04
 C32A-C29A \\sim C32B-C29B
 with sigma of 0.02
 C31A-C29A \\sim C31B-C29B
 with sigma of 0.04
 C32A-C34A \\sim C32B-C34B
 with sigma of 0.02
 C30A-C28A \\sim C30B-C28B
 with sigma of 0.04
 C32A-C33A \\sim C32B-C33B
 with sigma of 0.02
 C29A-C34A \\sim C29B-C34B
 with sigma of 0.04
 C29A-C28A \\sim C29B-C28B
 with sigma of 0.02
 C29A-C33A \\sim C29B-C33B
 with sigma of 0.04
 C27A-C28A \\sim C27B-C28B
 with sigma of 0.02
 C31A-C30A \\sim C31B-C30B
 with sigma of 0.02
 O8-C26 \\sim O00I-C26
 with sigma of 0.04
 O8-C28A \\sim O00I-C28B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim C35 \\sim Cl \\sim Cl3 \\sim C01D: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O8 \\sim C27A \\sim C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A
\\sim C34A \\sim O00I \\sim C27B \\sim C28B \\sim C29B \\sim C30B \\sim C31B
\\sim C32B \\sim C33B \\sim C34B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
4. 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
5. Others
 Fixed Sof: Cl1(0.88577) Cl2(0.88577) O8(0.55991) C27A(0.55991) C28A(0.55991)
 H28A(0.55991) H28B(0.55991) C29A(0.55991) H29A(0.55991) C30A(0.55991)
 H30A(0.55991) H30B(0.55991) C31A(0.55991) H31A(0.55991) H31B(0.55991)
 C32A(0.55991) C33A(0.55991) H33A(0.55991) H33B(0.55991) H33C(0.55991)
 C34A(0.55991) H34A(0.55991) H34B(0.55991) H34C(0.55991) C35(0.88577)
 H35A(0.88577) H35B(0.88577) Cl(0.11423) Cl3(0.11423) O00I(0.44009)
 C01D(0.11423) H01A(0.11423) H01B(0.11423) C27B(0.44009) C28B(0.44009)
 H28C(0.44009) H28D(0.44009) C29B(0.44009) H29B(0.44009) C30B(0.44009)
 H30C(0.44009) H30D(0.44009) C31B(0.44009) H31C(0.44009) H31D(0.44009)
 C32B(0.44009) C33B(0.44009) H33D(0.44009) H33E(0.44009) H33F(0.44009)
 C34B(0.44009) H34D(0.44009) H34E(0.44009) H34F(0.44009)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C29A(H29A), C29B(H29B)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C17(H17A,H17B), C25(H25A,
 H25B), C28A(H28A,H28B), C30A(H30A,H30B), C31A(H31A,H31B), C35(H35A,H35B),
 C01D(H01A,H01B), C28B(H28C,H28D), C30B(H30C,H30D), C31B(H31C,H31D)
6.c Me refined with riding coordinates:
 C33A(H33A,H33B,H33C), C34A(H34A,H34B,H34C), C33B(H33D,H33E,H33F), C34B(H34D,
 H34E,H34F)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C9(H9), C10(H10), C12(H12), C13(H13), C19(H19), C20(H20), C22(H22),
 C23(H23)
6.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              21630
_shelx_hkl_checksum              7563
_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 1.320
_oxdiff_exptl_absorpt_empirical_full_min 0.578