An Asymmetric Organocatalysis Approach to the Prenylated Alkaloid Family.
Rees, Matthew; Simpkins, Nigel S.; Male, Louise; Organic letters 19 (2017) 1338–1341; doi:10.1021/acs.orglett.7b00193

data_1545327
_publ_section_title
;
 An Asymmetric Organocatalysis Approach to the Prenylated Alkaloid Family.
;
_journal_issue                   6
_journal_name_full               'Organic letters'
_journal_page_first              1338
_journal_page_last               1341
_journal_paper_doi               10.1021/acs.orglett.7b00193
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H26 N2 O4, 0.5(C3 H8 O)'
_chemical_formula_sum            'C30.5 H30 N2 O4.5'
_chemical_formula_weight         496.56
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.73850(10)
_cell_length_b                   8.77985(12)
_cell_length_c                   65.4284(6)
_cell_measurement_reflns_used    35692
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      70.8230
_cell_measurement_theta_min      5.0830
_cell_volume                     5019.84(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3537
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9827
_diffrn_measurement_details
;
  1 omega -106.00  -35.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000 -178.0000  -30.0000 94

  2 omega -104.00  -35.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000    0.0000 92

  3 omega -104.00  -35.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -120.0000 92

  4 omega -104.00  -35.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -180.0000 92

  5 omega -157.00  -80.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -      -55.7969  -94.0000   90.0000 102

  6 omega -157.00  -10.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -      -55.7969  -61.0000  -30.0000 196

  7 omega  -96.00   -3.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -      -55.7969  125.0000  120.0000 124

  8 omega  -96.00   -3.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -      -55.7969  125.0000  -90.0000 124

  9 omega    7.00  152.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   45.0000 -180.0000 194

 10 omega    9.00  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000   60.0000 202

 11 omega   94.00  152.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969  125.0000 -180.0000 78

 12 omega   94.00  152.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969  125.0000   30.0000 78

 13 omega   57.00  177.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   38.0000  120.0000 160

 14 omega  100.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  111.0000  -30.0000 104

 15 omega  100.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  111.0000 -150.0000 104

 16 omega  100.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  111.0000   60.0000 104

 17 omega   13.00   94.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  -25.0000   30.0000 108

 18 omega   64.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000   90.0000 152

 19 omega   14.00  114.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939 -111.0000  -90.0000 134

 20 omega   64.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000 -150.0000 152

 21 omega   65.00  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   63.0000   60.0000 150

 22 omega   65.00  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   50.0000    0.0000 150

 23 omega   14.00   92.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  -38.0000  -30.0000 104

 24 omega   57.00  150.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  178.0000   90.0000 124

 25 omega   57.00  177.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   38.0000   60.0000 160

 26 omega   65.00  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   50.0000 -180.0000 150

 27 omega   65.00  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   63.0000   90.0000 150

 28 omega   57.00  123.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  178.0000    0.0000 88

 29 omega  -99.00  -83.25   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000   60.0000 21

 30 omega  -47.00   13.00   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 80

 31 omega -162.00 -114.75   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -      -55.7969  -77.0000  -90.0000 63

 32 omega   92.25  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000  120.0000 91

 33 omega  123.75  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000 -150.0000 49

 34 omega    9.00  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000 -120.0000 202

 35 omega  117.75  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000  -30.0000 57

 36 omega  110.25  160.50   0.7500    0.7500
omega____ theta____ kappa____ phi______ frames
    -       55.7969   77.0000  150.0000 67

 37 omega   76.75  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000  120.0000 135

 38 omega  112.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000  -60.0000 88

 39 omega  120.25  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000 -120.0000 77

 40 omega   14.00   87.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939 -111.0000   60.0000 98

 41 omega  112.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000  -30.0000 88

 42 omega  109.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000 -180.0000 92

 43 omega  115.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  111.0000  -90.0000 84

 44 omega  123.50  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   63.0000  -60.0000 72

 45 omega  101.50  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000   30.0000 102

 46 omega  122.75  177.50   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   50.0000  -60.0000 73

 47 omega   64.00  178.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939   77.0000    0.0000 152

 48 omega   57.00  150.00   0.7500    6.5800
omega____ theta____ kappa____ phi______ frames
    -      111.5939  178.0000  -90.0000 124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1663765000
_diffrn_orient_matrix_UB_12      -0.0513955000
_diffrn_orient_matrix_UB_13      -0.0035337000
_diffrn_orient_matrix_UB_21      -0.0181491000
_diffrn_orient_matrix_UB_22      0.1222206000
_diffrn_orient_matrix_UB_23      -0.0167348000
_diffrn_orient_matrix_UB_31      0.0551213000
_diffrn_orient_matrix_UB_32      -0.1150573000
_diffrn_orient_matrix_UB_33      -0.0161830000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       79
_diffrn_reflns_limit_l_min       -79
_diffrn_reflns_number            71872
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.124
_diffrn_reflns_theta_min         2.701
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.713
_exptl_absorpt_correction_T_max  0.990
_exptl_absorpt_correction_T_min  0.983
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.314
_exptl_crystal_description       block
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.3083
_exptl_crystal_size_mid          0.2449
_exptl_crystal_size_min          0.1824
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 3953 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     715
_refine_ls_number_reflns         9353
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0261P)^2^+4.8234P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1081
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                9294
_reflns_number_total             9353
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b00193_si_001.cif
_cod_data_source_block           18a
_cod_depositor_comments          'Adding full bibliography for 1545327.cif.'
_cod_original_formula_sum        'C30.50 H30 N2 O4.50'
_cod_database_code               1545327
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C29 H26 N2 O4'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.682(2) 0.318(2)
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, All O(H) groups
3. Restrained distances
 O2-H2
 0.9 with sigma of 0.03
4. Uiso/Uaniso restraints and constraints
C201 \\sim C21': within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(C21') \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
5. Others
 Sof(C21')=Sof(H21')=Sof(C22')=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23')=
 Sof(H23C)=Sof(H23D)=Sof(H23E)=Sof(O21')=Sof(H21A)=1-FVAR(1)
 Sof(C201)=Sof(H201)=Sof(C202)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C203)=
 Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(O201)=Sof(H20G)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C108(H108), C109(H109), C201(H201), C21'(H21')
6.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C23(H23A,H23B), C105(H10A,H10B),
 C106(H10C,H10D), C107(H10E,H10F), C123(H12A,H12B)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29),
  C112(H112), C113(H113), C114(H114), C115(H115), C116(H116), C118(H118),
 C119(H119), C120(H120), C121(H121), C122(H122), C125(H125), C126(H126),
 C127(H127), C128(H128), C129(H129)
6.d Tetrahedral OH refined with riding coordinates:
 O201(H20G), O21'(H21A)
6.e Idealised Me refined as rotating group:
 C202(H20A,H20B,H20C), C203(H20D,H20E,H20F), C22'(H22A,H22B,H22C), C23'(H23C,
 H23D,H23E)
;
_shelx_res_checksum              96367
_shelx_hkl_checksum              34112
_olex2_submission_special_instructions 'No special instructions were received'