Synthesis of chiral β-hydroxy allylic sulfides via iridium-catalyzed asymmetric cascade allylation/acyl transfer rearrangement
Wei, Jun; Yi, Zhi-Yuan; Jin, Zhuan; Liu, Yi; Wang, Zuo-Fei; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical Communications 61 (2025) 5609–5612; doi:10.1039/D5CC00422E

data_7134305
_publ_section_title
;
 Synthesis of chiral \b-hydroxy allylic sulfides via iridium-catalyzed
 asymmetric cascade allylation/acyl transfer rearrangement
;
_journal_issue                   30
_journal_name_full               'Chemical Communications'
_journal_page_first              5609
_journal_page_last               5612
_journal_paper_doi               10.1039/D5CC00422E
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H16 O4 S'
_chemical_formula_sum            'C16 H16 O4 S'
_chemical_formula_weight         4855.44
_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             2024-12-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-12-19 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.996(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   5.78780(10)
_cell_length_b                   33.2044(6)
_cell_length_c                   30.9443(5)
_cell_measurement_reflns_used    32163
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.6240
_cell_measurement_theta_min      2.7220
_cell_volume                     5946.89(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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    -45.00 -15.00   0.50    0.50    --    0.00 -77.00 -60.00   60
  2  \w    -10.00  15.00   0.50    0.50    --    0.00 -82.00  30.00   50
  3  \w    -42.00   2.00   0.50    0.50    --    0.00 -77.00   0.00   88
  4  \w    -31.00  27.00   0.50    0.50    --    0.00 -82.00-120.00  116
  5  \w     17.00  43.00   0.50    0.50    --    0.00  57.00 -90.00   52
  6  \w    -22.00  53.00   0.50    0.50    --    0.00  57.00 -30.00  150
  7  \w     80.00 127.00   0.50    1.00    --   95.20 -82.00 -90.00   94
  8  \w      6.00 103.00   0.50    1.00    --   95.20 -77.00  90.00  194
  9  \w     22.00  62.00   0.50    1.00    --   95.20 -77.00  30.00   80
 10  \w     51.00 105.00   0.50    1.00    --   95.20 -61.00  90.00  108
 11  \w      7.00  48.00   0.50    1.00    --   95.20 -61.00  90.00   82
 12  \w     24.00 123.00   0.50    1.00    --   95.20 -82.00-150.00  198
 13  \w     18.00 116.00   0.50    1.00    --   95.20 -61.00 -30.00  196
 14  \w     13.00 105.00   0.50    1.00    --   95.20 -82.00 150.00  184
 15  \w     12.00 112.00   0.50    1.00    --   95.20 -30.00-150.00  200
 16  \w     94.00 119.00   0.50    1.00    --   95.20 -82.00 -60.00   50
 17  \w      6.00  92.00   0.50    1.00    --   95.20 -15.00-120.00  172
 18  \w    136.00 178.00   0.50    1.00    --   95.20  30.00-180.00   84
 19  \w    117.00 143.00   0.50    1.00    --   95.20  82.00  60.00   52
 20  \w     84.00 110.00   0.50    1.00    --   95.20  30.00-180.00   52
 21  \w     83.00 109.00   0.50    1.00    --   95.20 -82.00 120.00   52
 22  \w     79.00 105.00   0.50    1.00    --   95.20 -77.00  30.00   52
 23  \w     73.00 181.00   0.50    1.00    --   95.20  15.00-150.00  216
 24  \w     16.00 104.00   0.50    1.00    --   95.20 -61.00-150.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0004114000
_diffrn_orient_matrix_UB_12      0.0451531000
_diffrn_orient_matrix_UB_13      -0.0114421000
_diffrn_orient_matrix_UB_21      -0.0524404000
_diffrn_orient_matrix_UB_22      0.0104948000
_diffrn_orient_matrix_UB_23      0.0474807000
_diffrn_orient_matrix_UB_31      0.2609513000
_diffrn_orient_matrix_UB_32      0.0020512000
_diffrn_orient_matrix_UB_33      0.0095768000
_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  0.0597
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            63590
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.251
_diffrn_reflns_theta_min         2.661
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.054
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40134
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
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    1.356
_exptl_crystal_description       needle
_exptl_crystal_F_000             2546
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.077
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Flack x determined using 8641 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1524
_refine_ls_number_reflns         21664
_refine_ls_number_restraints     1094
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0733
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0992P)^2^+12.4847P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1874
_refine_ls_wR_factor_ref         0.1909
_reflns_Friedel_coverage         0.951
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                21057
_reflns_number_total             21664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00422e2.cif
_cod_data_source_block           20241126_wj-5-1
_cod_depositor_comments
;

2025-03-31
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 7134305.cif.
;
_cod_original_formula_moiety     '14(C16 H16 O4 S), 2(C16 H15 O4 S)'
_cod_original_formula_sum        'C256 H242 O64 S16'
_cod_original_formula_units_Z    1
_cod_original_formula_weight     4855.44
_cod_database_code               7134305
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.821
_shelx_estimated_absorpt_t_min   0.427
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5666(19)
 0.4334(19)
2. 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
3. Rigid bond restraints
 C02A, S008
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C026 \\sim C00W \\sim C02U \\sim C01J \\sim C022 \\sim C01Q \\sim C014 \\sim
C00M \\sim C01L \\sim C00U: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O21 \\sim C01C \\sim H02K \\sim O02L \\sim C03Z: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C026 \\sim C00U \\sim C01L: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
Uanis(O02L) \\sim Ueq, Uanis(S008) \\sim Ueq, Uanis(O03V) \\sim Ueq,
Uanis(O041) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C03O)
\\sim Ueq, Uanis(C04J) \\sim Ueq, Uanis(C03B) \\sim Ueq, Uanis(C6) \\sim Ueq,
Uanis(C030) \\sim Ueq, Uanis(C04C) \\sim Ueq, Uanis(C049) \\sim Ueq,
Uanis(C037) \\sim Ueq, Uanis(C01C) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(C028)
\\sim Ueq, Uanis(C03X) \\sim Ueq, Uanis(C03Z) \\sim Ueq, Uanis(C03C) \\sim Ueq,
Uanis(C040) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C04G) \\sim Ueq, Uanis(S007) \\sim Ueq, Uanis(O00H) \\sim Ueq,
Uanis(C01X) \\sim Ueq, Uanis(O027) \\sim Ueq, Uanis(C03M) \\sim Ueq,
Uanis(C02W) \\sim Ueq, Uanis(C02T) \\sim Ueq, Uanis(C01N) \\sim Ueq,
Uanis(C02S) \\sim Ueq, Uanis(O00S) \\sim Ueq, Uanis(C04H) \\sim Ueq,
Uanis(O031) \\sim Ueq, Uanis(C02Q) \\sim Ueq, Uanis(C02E) \\sim Ueq,
Uanis(C01Y) \\sim Ueq, Uanis(C04I) \\sim Ueq, Uanis(C011) \\sim Ueq,
Uanis(C00Q) \\sim Ueq, Uanis(C00Z) \\sim Ueq, Uanis(C01I) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O02D) \\sim Ueq, Uanis(S005) \\sim Ueq, Uanis(O00R) \\sim Ueq,
Uanis(O01B) \\sim Ueq, Uanis(C022) \\sim Ueq, Uanis(C048) \\sim Ueq,
Uanis(C01J) \\sim Ueq, Uanis(C01Q) \\sim Ueq, Uanis(C02M) \\sim Ueq,
Uanis(C04D) \\sim Ueq, Uanis(C02U) \\sim Ueq, Uanis(C014) \\sim Ueq,
Uanis(C00M) \\sim Ueq, Uanis(C00W) \\sim Ueq, Uanis(O00P) \\sim Ueq,
Uanis(C03Q) \\sim Ueq, Uanis(C02X) \\sim Ueq, Uanis(C01L) \\sim Ueq,
Uanis(C026) \\sim Ueq, Uanis(C04F) \\sim Ueq, Uanis(C00U) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(S003) \\sim Ueq, Uanis(O00C) \\sim Ueq, Uanis(O00N) \\sim Ueq,
Uanis(C046) \\sim Ueq, Uanis(C02Y) \\sim Ueq, Uanis(C03D) \\sim Ueq,
Uanis(C016) \\sim Ueq, Uanis(C036) \\sim Ueq, Uanis(C033) \\sim Ueq,
Uanis(O01E) \\sim Ueq, Uanis(C02R) \\sim Ueq, Uanis(C03S) \\sim Ueq,
Uanis(C01M) \\sim Ueq, Uanis(C02Z) \\sim Ueq, Uanis(C02C) \\sim Ueq,
Uanis(O00T) \\sim Ueq, Uanis(C017) \\sim Ueq, Uanis(C03P) \\sim Ueq,
Uanis(C02V) \\sim Ueq, Uanis(C02G) \\sim Ueq, Uanis(C038) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C01R) \\sim Ueq, Uanis(S004) \\sim Ueq, Uanis(O00D) \\sim Ueq,
Uanis(O00G) \\sim Ueq, Uanis(C01P) \\sim Ueq, Uanis(C02P) \\sim Ueq,
Uanis(C03I) \\sim Ueq, Uanis(C025) \\sim Ueq, Uanis(C03U) \\sim Ueq,
Uanis(C044) \\sim Ueq, Uanis(C04E) \\sim Ueq, Uanis(C02N) \\sim Ueq,
Uanis(C03N) \\sim Ueq, Uanis(C013) \\sim Ueq, Uanis(O00V) \\sim Ueq,
Uanis(C045) \\sim Ueq, Uanis(C02H) \\sim Ueq, Uanis(C02F) \\sim Ueq,
Uanis(O012) \\sim Ueq, Uanis(C043) \\sim Ueq, Uanis(C03T) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C024) \\sim Ueq, Uanis(S002) \\sim Ueq, Uanis(O00A) \\sim Ueq,
Uanis(O00B) \\sim Ueq, Uanis(C01K) \\sim Ueq, Uanis(C034) \\sim Ueq,
Uanis(C01D) \\sim Ueq, Uanis(C03A) \\sim Ueq, Uanis(C029) \\sim Ueq,
Uanis(C01F) \\sim Ueq, Uanis(C010) \\sim Ueq, Uanis(C00X) \\sim Ueq,
Uanis(C03J) \\sim Ueq, Uanis(O00F) \\sim Ueq, Uanis(C00L) \\sim Ueq,
Uanis(C018) \\sim Ueq, Uanis(C03G) \\sim Ueq, Uanis(O01Z) \\sim Ueq,
Uanis(C00Y) \\sim Ueq, Uanis(C01V) \\sim Ueq, Uanis(C042) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O035) \\sim Ueq, Uanis(S001) \\sim Ueq, Uanis(O009) \\sim Ueq,
Uanis(O00I) \\sim Ueq, Uanis(C01W) \\sim Ueq, Uanis(C020) \\sim Ueq,
Uanis(C02I) \\sim Ueq, Uanis(C03K) \\sim Ueq, Uanis(C01O) \\sim Ueq,
Uanis(C01U) \\sim Ueq, Uanis(C02O) \\sim Ueq, Uanis(O015) \\sim Ueq,
Uanis(C00K) \\sim Ueq, Uanis(C00E) \\sim Ueq, Uanis(C01H) \\sim Ueq,
Uanis(C04B) \\sim Ueq, Uanis(C01S) \\sim Ueq, Uanis(C02J) \\sim Ueq,
Uanis(C03Y) \\sim Ueq, Uanis(C01G) \\sim Ueq, Uanis(C02K) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O019) \\sim Ueq, Uanis(S006) \\sim Ueq, Uanis(O00J) \\sim Ueq,
Uanis(C021) \\sim Ueq, Uanis(C03W) \\sim Ueq, Uanis(C01A) \\sim Ueq,
Uanis(C01T) \\sim Ueq, Uanis(C023) \\sim Ueq, Uanis(C047) \\sim Ueq,
Uanis(C03R) \\sim Ueq, Uanis(C03H) \\sim Ueq, Uanis(C03L) \\sim Ueq,
Uanis(O00O) \\sim Ueq, Uanis(C04A) \\sim Ueq, Uanis(C03E) \\sim Ueq,
Uanis(C02B) \\sim Ueq, Uanis(C03F) \\sim Ueq, Uanis(C04M) \\sim Ueq,
Uanis(C039) \\sim Ueq, Uanis(C032) \\sim Ueq, Uanis(O04K) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(O21) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C01T) \\sim Ueq, Uanis(C03H) \\sim Ueq, Uanis(C01A) \\sim Ueq,
Uanis(C03L) \\sim Ueq, Uanis(C03R) \\sim Ueq, Uanis(C03M) \\sim Ueq,
Uanis(C042) \\sim Ueq, Uanis(C03K) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C00W) \\sim Ueq, Uanis(C026) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S007) \\sim Ueq, Uanis(S008) \\sim Ueq, Uanis(C04I) \\sim Ueq,
Uanis(C03M) \\sim Ueq, Uanis(C02E) \\sim Ueq, Uanis(C01Y) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C01Y) \\sim Ueq, Uanis(C02E) \\sim Ueq, Uanis(C03M) \\sim Ueq,
Uanis(C02T) \\sim Ueq, Uanis(C00Z) \\sim Ueq, Uanis(C02O) \\sim Ueq,
Uanis(C03N) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O035) \\sim Ueq, Uanis(C04M) \\sim Ueq, Uanis(C02O) \\sim Ueq,
Uanis(C026) \\sim Ueq, Uanis(O03V) \\sim Ueq, Uanis(S008) \\sim Ueq,
Uanis(O041) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O00P) \\sim Ueq, Uanis(C026) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C026) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5.a Ternary CH refined with riding coordinates:
 C01W(H01W), C01X(H01X), C02P(H02Q), C034(H034), C03W(H03), C046(H046),
 C048(H048), C8(H8)
5.b Secondary CH2 refined with riding coordinates:
 C029(H02C,H02D), C02M(H02S,H02T), C03D(H03I,H03J), C03K(H03A,H03B), C044(H04G,
 H04H), C04G(H04O,H04P), C6(H6A,H6B)
5.c Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00L(H00L), C00M(H00M), C00Q(H00Q), C00U(H00U), C00Y(H00Y),
 C00Z(H00Z), C010(H010), C011(H011), C016(H016), C017(H017), C018(H018),
 C01A(H01A), C01D(H01D), C01G(H01G), C01I(H01I), C01J(H01J), C01L(H01L),
 C01N(H01N), C01O(H01O), C01Q(H01Q), C01S(H01S), C01T(H01T), C01U(H01U),
 C01V(H01V), C023(H023), C024(H024), C025(H025), C026(H026), C028(H028),
 C02B(H02), C02F(H02N), C02G(H02G), C02H(H02O), C02I(H02I), C02J(H02J),
 C02K(H02K), C02N(H02P), C02Q(H02V), C02R(H02R), C02T(H02Y), C02U(H02U),
 C02W(H02Z), C030(H030), C032(H032), C033(H033), C036(H036), C038(H038),
 C039(H039), C03A(H03F), C03B(H03O), C03C(H03Q), C03E(H03Y), C03H(H03Z),
 C03I(H03K), C03N(H03N), C03O(H03R), C03P(H03P), C03T(H03T), C03U(H03U),
 C03X(H03X), C040(H040), C047(H047), C04D(H04K), C04J(H04V)
5.d X=CH2 refined with riding coordinates:
 C02O(H02A,H02B), C02S(H02W,H02X), C02Z(H02L,H02M), C03J(H03G,H03H), C03Q(H03L,
 H03M), C04A(H04W,H04X), C04C(H04T,H04U), C04E(H04I,H04J)
5.e Idealised Me refined as rotating group:
 C02V(H02E,H02F,H02H), C03Y(H03C,H03D,H03E), C03Z(H03S,H03V,H03W), C042(H04A,
 H04B,H04C), C043(H04D,H04E,H04F), C04F(H04L,H04M,H04N), C04I(H04Q,H04R,H04S),
 C04M(H04Y,H,HA)
;
_shelx_res_checksum              42669
_shelx_hkl_checksum              4110
_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 2.539
_oxdiff_exptl_absorpt_empirical_full_min 0.432