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_7134725
_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 unk
_chemical_formula_moiety         'C21 H26 O3'
_chemical_formula_sum            'C21 H26 O3'
_chemical_formula_weight         326.439
_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'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2m51hc
_audit_creation_date             2025-01-07
_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                 99.133(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.3186(8)
_cell_length_b                   10.0507(8)
_cell_length_c                   10.7125(11)
_cell_measurement_reflns_used    9691
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      25.352
_cell_measurement_theta_min      2.889
_cell_volume                     884.29(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 0.9976
_diffrn_measured_fraction_theta_max 0.9971
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 0.9976
_diffrn_reflns_Laue_measured_fraction_max 0.9971
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            48959
_diffrn_reflns_point_group_measured_fraction_full 0.9950
_diffrn_reflns_point_group_measured_fraction_max 0.9945
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         25.37
_diffrn_reflns_theta_min         1.93
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.080
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9378
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1031 before and 0.0606 after correction.
The Ratio of minimum to maximum transmission is 0.9378.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       block
_exptl_crystal_F_000             352.214
_refine_diff_density_max         0.1748
_refine_diff_density_min         -0.1506
_refine_diff_density_rms         0.0298
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   0.02(15)
_refine_ls_d_res_high            0.8295
_refine_ls_d_res_low             10.5767
_refine_ls_extinction_coef       0.023(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.1118
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    39
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3229
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.1118
_refine_ls_R_factor_all          0.0251
_refine_ls_R_factor_gt           0.0250
_refine_ls_shift/su_max          -0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+0.1389P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0671
_refine_ls_wR_factor_ref         0.0672
_reflns_Friedel_coverage         0.991
_reflns_limit_h_max              9
_reflns_limit_h_min              -10
_reflns_limit_k_max              12
_reflns_limit_k_min              -12
_reflns_limit_l_max              12
_reflns_limit_l_min              -12
_reflns_number_gt                3208
_reflns_number_total             3229
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc02354h2.cif
_cod_data_source_block           AB_RAM_264
_cod_depositor_comments
'Adding full bibliography for 7134724--7134725.cif.'
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               7134725
_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:
 C00L(H00o)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00e,H00g), C00I(H00k,H00l), C00K(H00m,H00n)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00F(H00F), C008(H008)
2.d Idealised Me refined as rotating group:
 C00D(H00b,H00c,H00d), C00H(H00h,H00i,H00j), C00M(H00p,H00q,H00r), C00N(H00s,
 H00t,H00u), C00O(H00v,H00w,H00x)
;
_olex2_submission_special_instructions 'No special instructions were received'