Site-selective C–H alkylation of myo-inositol via organic photoredox catalysis
Cao, Haonan; Guo, Tianyun; Deng, Xuemei; Huo, Xing; Tang, Shouchu; Liu, Jian; Wang, Xiaolei; Chemical Communications  (2022) –; doi:10.1039/D2CC03569C

data_7130562
_publ_section_title
;
 Site-selective C--H alkylation of myo-inositol via organic photoredox
 catalysis
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03569C
_journal_year                    2022
_chemical_formula_moiety         'C23 H29 N O11'
_chemical_formula_sum            'C23 H29 N O11'
_chemical_formula_weight         495.47
_chemical_name_systematic
'(1R,2R,3R,4R,5S,6S)-6-hydroxy-6-(2-(pyridin-2-yl)ethyl)cyclohexane-1,2,3,4,5-pentayl pentaacetate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc29wc5r
_audit_creation_date             2021-09-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-01-12 deposited with the CCDC.	2022-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                96.0575(7)
_cell_angle_beta                 90.7961(7)
_cell_angle_gamma                107.8097(8)
_cell_formula_units_Z            2
_cell_length_a                   9.59580(9)
_cell_length_b                   11.62912(10)
_cell_length_c                   11.80883(10)
_cell_measurement_reflns_used    28120
_cell_measurement_temperature    294.4(6)
_cell_measurement_theta_max      76.3820
_cell_measurement_theta_min      3.7670
_cell_volume                     1246.12(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      294.4(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.945
_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     28.00  56.00   0.50    0.05    --   46.32  74.00 -26.00   56
  2  \w     25.00  51.00   0.50    0.05    --   46.32  77.00-120.00   52
  3  \w     60.00  87.00   0.50    0.05    --   46.32  74.00 -26.00   54
  4  \w     28.00  54.00   0.50    0.05    --   50.00  76.00  12.01   52
  5  \w     27.00  53.00   0.50    0.05    --   46.32  77.00 150.00   52
  6  \w     34.00  63.00   0.50    0.05    --   46.32  37.00  90.00   58
  7  \w     79.00 115.00   0.50    0.05    --  104.25-132.00 152.81   72
  8  \w     41.00  84.00   0.50    0.05    --  104.25-125.00  90.00   86
  9  \w     42.00  72.00   0.50    0.05    --  104.25-125.00  30.00   60
 10  \w     38.00 104.00   0.50    0.05    --  104.25-125.00 120.00  132
 11  \w     33.00 102.00   0.50    0.05    --  104.25 -94.00 120.00  138
 12  \w     79.00 111.00   0.50    0.05    --  104.25-125.00  30.00   64
 13  \w     39.00 112.00   0.50    0.05    --  104.25-125.00   0.00  146
 14  \w     35.00 111.00   0.50    0.05    --  104.25-125.00-120.00  152
 15  \w     74.00 101.00   0.50    0.05    --  104.25 -94.00-150.00   54
 16  \w    -21.00  68.00   0.50    0.05    --   46.32 -74.00-154.00  178
 17  \w     35.00  63.00   0.50    0.05    --  104.25 -61.00-120.00   56
 18  \w     63.00  91.00   0.50    0.05    --  104.25 -74.00-154.00   56
 19  \w     48.00  73.00   0.50    0.05    --  104.25 -61.00 -30.00   50
 20  \w     32.00  67.00   0.50    0.05    --  104.25 -61.00   0.00   70
 21  \w     48.00  73.00   0.50    0.05    --  104.25 -61.00  30.00   50
 22  \w     31.00  60.00   0.50    0.05    --   54.00  77.00-104.89   58
 23  \w     47.00  73.00   0.50    0.05    --   70.00  77.00-164.14   52
 24  \w     31.00  76.00   0.50    0.05    --   54.00  77.00  16.79   90
 25  \w     35.00  61.00   0.50    0.05    --   58.00  77.00  46.06   52
 26  \w     44.00  69.00   0.50    0.05    --   66.00  76.00  64.25   50
 27  \w     36.00  62.00   0.50    0.05    --   54.00  75.00 119.29   52
 28  \w     93.00 126.00   0.50    0.05    --   54.00  75.00 119.29   66
 29  \w     33.00  58.00   0.50    0.05    --   54.00  74.00 173.31   50
 30  \w    139.00 165.00   0.50    0.05    --  104.25  74.00 -26.00   52
 31  \w     87.00 134.00   0.50    0.05    --  104.25  74.00 -26.00   94
 32  \w     82.00 126.00   0.50    0.05    --   54.00  75.00-155.25   88
 33  \w     35.00  61.00   0.50    0.05    --   54.00  75.00-155.25   52
 34  \w     38.00  72.00   0.50    0.05    --   58.00  75.00 -84.45   68
 35  \w     33.00  58.00   0.50    0.05    --   54.00  73.00  93.20   50
 36  \w      7.00  40.00   0.50    0.05    --   30.00  87.00 119.92   66
 37  \w      9.00  34.00   0.50    0.05    --   38.00  91.00  31.17   50
 38  \w     -7.00  19.00   0.50    0.05    --   26.00 100.00 -39.73   52
 39  \w     14.00  39.00   0.50    0.05    --   42.00  89.00 -79.04   50
 40  \w    -14.00  11.00   0.50    0.05    --   18.00  98.00-162.76   50
 41  \w    -16.00  25.00   0.50    0.05    --  -46.32  74.00 -26.00   82
 42  \w    -63.00 -31.00   0.50    0.05    --  -46.32  74.00 -26.00   64
 43  \w    -90.00 -55.00   0.50    0.05    -- -102.00  74.00 -26.00   70
 44  \w    -69.00 -32.00   0.50    0.05    -- -102.00  61.00-180.00   74
 45  \w   -118.00 -84.00   0.50    0.05    --  -46.32 -19.00 -30.00   68
 46  \w    -79.00 -43.00   0.50    0.05    --  -46.32 -19.00 -30.00   72
 47  \w    -60.00 -34.00   0.50    0.05    --  -46.32 -37.00  60.00   52
 48  \w   -112.00 -55.00   0.50    0.05    -- -102.00 125.00 -90.00  114
 49  \w   -122.00 -37.00   0.50    0.05    -- -102.00 139.00 112.44  170
 50  \w    -50.00 -25.00   0.50    0.05    --  -46.32 -74.00-154.00   50
 51  \w   -174.00 -82.00   0.50    0.05    -- -102.00 -79.00 -98.41  184
 52  \w   -142.00-116.00   0.50    0.05    --  -70.00 -77.00-121.84   52
 53  \w    -73.00 -47.00   0.50    0.05    --  -70.00 -77.00-121.84   52
 54  \w    -76.00 -51.00   0.50    0.05    --  -74.00 -77.00 -97.47   50
 55  \w   -128.00 -79.00   0.50    0.05    -- -102.00 -77.00 -29.12   98
 56  \w    -72.00 -47.00   0.50    0.05    --  -70.00 -77.00   1.06   50
 57  \w    -72.00 -47.00   0.50    0.05    --  -70.00 -76.00  74.15   50
 58  \w    -70.00 -43.00   0.50    0.05    --  -66.00 -77.00 111.25   54
 59  \w    -97.00 -68.00   0.50    0.05    --  -90.00 -76.00 156.02   58
 60  \w   -160.00-113.00   0.50    0.05    --  -90.00 -76.00 156.02   94
 61  \w   -139.00-114.00   0.50    0.05    --  -66.00 -77.00 111.25   50
 62  \w   -104.00 -76.00   0.50    0.05    --  -98.00 -76.00 100.30   56
 63  \w   -121.00 -71.00   0.50    0.05    --  -94.00 -76.00  58.13  100
 64  \w   -170.00-109.00   0.50    0.05    --  -98.00 -76.00 100.30  122
 65  \w   -140.00-115.00   0.50    0.05    --  -70.00 -76.00  74.15   50
 66  \w   -140.00-114.00   0.50    0.05    --  -70.00 -76.00 142.04   52
 67  \w   -113.00 -71.00   0.50    0.05    --  -94.00 -76.00  12.07   84
 68  \w   -145.00 -79.00   0.50    0.05    -- -102.00 -76.00 -46.45  132
 69  \w   -174.00-131.00   0.50    0.05    -- -102.00 -77.00 -29.12   86
 70  \w   -153.00 -71.00   0.50    0.05    --  -94.00 -76.00-167.78  164
 71  \w    -81.00 -56.00   0.50    0.05    --  -78.00 -75.00 -20.40   50
 72  \w    -87.00 -61.00   0.50    0.05    --  -82.00 -73.00 -54.56   52
 73  \w   -168.00-139.00   0.50    0.05    -- -102.00 -74.00-154.00   58
 74  \w    -99.00 -61.00   0.50    0.05    --  -82.00 -73.00 -39.05   76
 75  \w    -89.00 -64.00   0.50    0.05    --  -86.00 -74.00   0.52   50
 76  \w    -95.00 -70.00   0.50    0.05    --  -90.00 -73.00 114.17   50
 77  \w    -72.00 -47.00   0.50    0.05    --  -70.00 -76.00 142.04   50
 78  \w    -86.00 -61.00   0.50    0.05    --  -82.00 -73.00 113.91   50
 79  \w    -90.00 -65.00   0.50    0.05    --  -86.00 -73.00  61.11   50
 80  \w    -93.00 -65.00   0.50    0.05    --  -86.00 -74.00  27.49   56
 81  \w   -136.00-110.00   0.50    0.05    --  -86.00 -73.00  61.11   52
 82  \w   -149.00-121.00   0.50    0.05    --  -90.00 -72.00 129.71   56
 83  \w   -162.00 -99.00   0.50    0.05    --  -90.00 -72.00  38.19  126
 84  \w   -114.00 -69.00   0.50    0.05    --  -90.00 -72.00 129.71   90
 85  \w   -102.00 -69.00   0.50    0.05    --  -90.00 -72.00-134.05   66
 86  \w    -87.00 -61.00   0.50    0.05    --  -82.00 -73.00-159.05   52
 87  \w   -132.00 -69.00   0.50    0.05    --  -90.00 -72.00-163.36  126
 88  \w   -161.00-114.00   0.50    0.05    --  -90.00 -72.00-134.05   94
 89  \w   -139.00 -72.00   0.50    0.05    --  -90.00 -72.00 -81.11  134
 90  \w    -89.00 -50.00   0.50    0.05    --  -70.00 -70.00 -82.42   78
 91  \w   -142.00 -95.00   0.50    0.05    --  -70.00 -70.00 -82.42   94
 92  \w    -75.00 -50.00   0.50    0.05    --  -70.00 -69.00 -63.74   50
 93  \w    -94.00 -69.00   0.50    0.05    --  -90.00 -72.00  38.19   50
 94  \w   -162.00-113.00   0.50    0.05    --  -90.00 -68.00 -18.19   98
 95  \w   -175.00-116.00   0.50    0.05    -- -102.00 -68.00  88.29  118
 96  \w   -127.00 -82.00   0.50    0.05    -- -102.00 -70.00 113.78   90
 97  \w   -155.00 -69.00   0.50    0.05    --  -90.00 -72.00 168.27  172
 98  \w   -165.00 -78.00   0.50    0.05    --  -98.00 -71.00 147.94  174
 99  \w   -102.00 -71.00   0.50    0.05    --  -90.00 -68.00 -18.19   62
100  \w    -89.00 -63.00   0.50    0.05    --  -82.00 -67.00-114.48   52
101  \w    -82.00 -55.00   0.50    0.05    --  -74.00 -67.00-160.05   54
102  \w   -153.00-125.00   0.50    0.05    --  -82.00 -67.00-114.48   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1345989000
_diffrn_orient_matrix_UB_12      0.0458618000
_diffrn_orient_matrix_UB_13      0.0007622000
_diffrn_orient_matrix_UB_21      -0.0504621000
_diffrn_orient_matrix_UB_22      -0.0618493000
_diffrn_orient_matrix_UB_23      0.1079115000
_diffrn_orient_matrix_UB_31      0.0885437000
_diffrn_orient_matrix_UB_32      0.1170166000
_diffrn_orient_matrix_UB_33      0.0748760000
_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  0.0257
_diffrn_reflns_av_unetI/netI     0.0111
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            35365
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.235
_diffrn_reflns_theta_min         3.769
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.899
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70407
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             524
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-Hexane and dichloromethane'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.461
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.0109(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     323
_refine_ls_number_reflns         4922
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0458
_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^)+(0.0520P)^2^+0.4289P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4639
_reflns_number_total             4922
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03569c2.cif
_cod_data_source_block           caohn_0825_auto
_cod_database_code               7130562
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 99.37
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              16817
_shelx_hkl_checksum              1383
_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 1.516
_oxdiff_exptl_absorpt_empirical_full_min 0.637