Asymmetric total syntheses of immunosuppressive diterpenoids triptobenzenes N and R <i>via</i> a remote Csp<sup>3</sup>-H functionalization.
Roy, Nanda Kishore; Murmu, Ranjit; Munda, Mintu; Niyogi, Sovan; Bisai, Alakesh; Chemical communications (Cambridge, England) 61 (2025) 11053–11056; doi:10.1039/d5cc02354h

data_7134724
_publ_section_title
;
 Asymmetric total syntheses of immunosuppressive diterpenoids
 triptobenzenes N and R <i>via</i> a remote Csp<sup>3</sup>-H
 functionalization.
;
_journal_issue                   59
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11053
_journal_page_last               11056
_journal_paper_doi               10.1039/d5cc02354h
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration '4S 5R 6R 10S'
_chemical_formula_moiety         'C21 H27 Br O3'
_chemical_formula_sum            'C21 H27 Br O3'
_chemical_formula_weight         407.33
_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_block_doi                 10.5517/ccdc.csd.cc2lxw7n
_audit_creation_date             2024-12-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-18 deposited with the CCDC.	2025-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.010(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.3749(2)
_cell_length_b                   8.41780(10)
_cell_length_c                   11.3443(2)
_cell_measurement_reflns_used    8681
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.2080
_cell_measurement_theta_min      3.9180
_cell_volume                     975.66(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.989
_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    -64.00  28.00   0.50    0.20    --  -40.46  66.00-180.00  184
  2  \w    -64.00  28.00   0.50    0.20    --  -40.46  66.00-180.00  184
  3  \w     41.00 100.00   0.50    0.20    --   40.46-139.00  30.00  118
  4  \w    -28.00  31.00   0.50    0.20    --  -40.46  21.00  30.00  118
  5  \w    -41.00  26.00   0.50    0.20    --  -40.46  36.00 -56.00  134
  6  \w    -41.00  26.00   0.50    0.20    --  -40.46  36.00 -56.00  134
  7  \w    -61.00  27.00   0.50    0.20    --  -40.46  54.00 150.00  176
  8  \w    -61.00  27.00   0.50    0.20    --  -40.46  54.00 150.00  176
  9  \w   -107.00 -26.00   0.50    0.20    --  -40.46 -36.00 147.00  162
 10  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00   0.00  192
 11  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00 -30.00  192
 12  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00 -60.00  192
 13  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00-180.00  192
 14  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00-120.00  192
 15  \w   -108.00 -17.00   0.50    0.20    --  -40.46 -66.00  30.00  182
 16  \w   -108.00 -17.00   0.50    0.20    --  -40.46 -66.00  60.00  182
 17  \w   -109.00 -13.00   0.50    0.20    --  -40.46 -77.00 120.00  192
 18  \w   -107.00 -20.00   0.50    0.20    --  -40.46 -54.00  90.00  174
 19  \w   -107.00 -26.00   0.50    0.20    --  -40.46 -36.00 147.00  162
 20  \w    -47.00 -15.00   0.50    0.27    --  -82.50  42.00  60.00   64
 21  \w    -47.00 -15.00   0.50    0.27    --  -82.50  42.00 150.00   64
 22  \w   -149.00 -68.00   0.50    0.27    --  -82.50 -36.00 147.00  162
 23  \w   -108.00 -63.00   0.50    0.20    --  -40.46-139.00  90.00   90
 24  \w   -146.00 -78.00   0.50    0.27    --  -82.50-117.00 -90.00  136
 25  \w   -108.00 -63.00   0.50    0.20    --  -40.46-139.00 -60.00   90
 26  \w     28.00 105.00   0.50    0.27    --   96.67 -77.00 -30.00  154
 27  \w     28.00 105.00   0.50    0.27    --   96.67 -77.00 -30.00  154
 28  \w     29.00  83.00   0.50    0.27    --   96.67 -68.00 -30.00  108
 29  \w     29.00  83.00   0.50    0.27    --   96.67 -68.00  30.00  108
 30  \w     29.00  83.00   0.50    0.27    --   96.67 -68.00   0.00  108
 31  \w     29.00  83.00   0.50    0.27    --   96.67 -68.00 120.00  108
 32  \w     29.00  83.00   0.50    0.27    --   96.67 -68.00-120.00  108
 33  \w     29.00  68.00   0.50    0.27    --   96.67 -59.00-150.00   78
 34  \w     28.00 105.00   0.50    0.27    --   96.67 -77.00-180.00  154
 35  \w     28.00 105.00   0.50    0.27    --   96.67 -77.00-180.00  154
 36  \w     30.00  57.00   0.50    0.27    --   96.67 -50.00-180.00   54
 37  \w     30.00  57.00   0.50    0.27    --   96.67 -50.00-150.00   54
 38  \w     29.00  68.00   0.50    0.27    --   96.67 -59.00 -90.00   78
 39  \w     30.00  57.00   0.50    0.27    --   96.67 -50.00  30.00   54
 40  \w     29.00  68.00   0.50    0.27    --   96.67 -59.00  60.00   78
 41  \w     30.00  57.00   0.50    0.27    --   96.67 -50.00 150.00   54
 42  \w     75.00 164.00   0.50    0.27    --   96.67  59.00   0.00  178
 43  \w     82.00 163.00   0.50    0.27    --   96.67  36.00 -56.00  162
 44  \w     80.00 163.00   0.50    0.27    --   96.67  42.00  60.00  166
 45  \w     80.00 163.00   0.50    0.27    --   96.67  42.00  60.00  166
 46  \w     83.00 164.00   0.50    0.27    --   96.67  33.00 -30.00  162
 47  \w     82.00 163.00   0.50    0.27    --   96.67  36.00 -56.00  162
 48  \w     26.00 107.00   0.50    0.20    --   40.46  36.00 -56.00  162
 49  \w     26.00 107.00   0.50    0.20    --   40.46  36.00 -56.00  162
 50  \w    -31.00  28.00   0.50    0.20    --   40.46 -21.00  30.00  118
 51  \w    -26.00  41.00   0.50    0.20    --   40.46 -36.00 147.00  134
 52  \w    105.00 170.00   0.50    0.27    --   96.67  96.00 -60.00  130
 53  \w     99.00 161.00   0.50    0.27    --   96.67 117.00-150.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1276096000
_diffrn_orient_matrix_UB_12      -0.0585098000
_diffrn_orient_matrix_UB_13      0.0374200000
_diffrn_orient_matrix_UB_21      -0.0483885000
_diffrn_orient_matrix_UB_22      -0.0606572000
_diffrn_orient_matrix_UB_23      -0.1283353000
_diffrn_orient_matrix_UB_31      0.0639445000
_diffrn_orient_matrix_UB_32      -0.1623850000
_diffrn_orient_matrix_UB_33      0.0343858000
_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  0.0482
_diffrn_reflns_av_unetI/netI     0.0358
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            12092
_diffrn_reflns_point_group_measured_fraction_full 0.856
_diffrn_reflns_point_group_measured_fraction_max 0.847
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.347
_diffrn_reflns_theta_min         3.957
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.996
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74487
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.119a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             424
_refine_diff_density_max         0.605
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 1057 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3034
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0374
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+0.0494P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1001
_reflns_Friedel_coverage         0.595
_reflns_Friedel_fraction_full    0.693
_reflns_Friedel_fraction_max     0.682
_reflns_number_gt                2919
_reflns_number_total             3034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02354h2.cif
_cod_data_source_block           ab_ram_252_auto
_cod_depositor_comments
'Adding full bibliography for 7134724--7134725.cif.'
_cod_database_code               7134724
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O Br'
_chemical_oxdiff_usercomment     LT
_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:
 C00F(H00F), C00H(H00H), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00a,H00b), C00J(H00g,H00j), C00N(H00r,H00s)
2.c Aromatic/amide H refined with riding coordinates:
 C005(H005), C008(H008), C00K(H00K)
2.d Idealised Me refined as rotating group:
 C00G(H00c,H00d,H00e), C00L(H00l,H00m,H00n), C00M(H00o,H00p,H00q), C00O(H00t,
 H00u,H00v), C00P(H00w,H00x,H00y)
;
_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 0.771