Efficient and Divergent Total Synthesis of (-)-Epicoccin G and (-)-Rostratin A Enabled by Double C(sp<sup>3</sup>)-H Activation.
Thesmar, Pierre; Baudoin, Olivier; Journal of the American Chemical Society 141 (2019) 15779–15783; doi:10.1021/jacs.9b09359

data_4128302
_publ_section_title
;
 Efficient and Divergent Total Synthesis of (-)-Epicoccin G and
 (-)-Rostratin A Enabled by Double C(sp<sup>3</sup>)-H Activation.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15779
_journal_page_last               15783
_journal_paper_doi               10.1021/jacs.9b09359
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H30 N2 O8, 0.5(H1.5 O0.75)'
_chemical_formula_sum            'C22 H30.75 N2 O8.38'
_chemical_formula_weight         457.23
_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_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-10
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.057(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2836(19)
_cell_length_b                   9.5130(13)
_cell_length_c                   17.387(3)
_cell_measurement_reflns_used    9933
_cell_measurement_temperature    130
_cell_measurement_theta_max      70.047
_cell_measurement_theta_min      5.301
_cell_volume                     2197.1(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            36080
_diffrn_reflns_point_group_measured_fraction_full 0.794
_diffrn_reflns_point_group_measured_fraction_max 0.770
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.488
_diffrn_reflns_theta_min         3.327
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.890
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.7160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0485 before and 0.0352 after correction.
The Ratio of minimum to maximum transmission is 0.9505.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       block
_exptl_crystal_F_000             975
_exptl_crystal_recrystallization_method
'The material was recrystallised from AcOEt by slow evaporation'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.150
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2085 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     606
_refine_ls_number_reflns         6478
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0272
_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^)+(0.0449P)^2^+0.4101P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0724
_refine_ls_wR_factor_ref         0.0724
_reflns_Friedel_coverage         0.483
_reflns_Friedel_fraction_full    0.563
_reflns_Friedel_fraction_max     0.536
_reflns_number_gt                6459
_reflns_number_total             6478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09359_si_004.cif
_cod_data_source_block           thp1957p1_130k_0m
_cod_original_cell_volume        2197.2(5)
_cod_database_code               4128302
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.842
_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. Restrained distances
 O1-H1D = O1-H1E
 0.95 with sigma of 0.02
 O1-H1D = O1-H1E = O1-H1F
 0.9 with sigma of 0.02
3. Others
 Fixed Sof: O1(0.75) H1D(0.375) H1E(0.375) H1F(0.75)
4.a Ternary CH refined with riding coordinates:
 C39(H39), C26(H26), C27(H27), C38(H38), C4(H4A), C29(H29), C5(H5), C35(H35),
 C13(H13), C3(H3), C16(H16), C25(H25), C31(H31), C15(H15A), C42(H42), C19(H19),
 C20(H20), C7(H7A), C37(H37), C9(H9)
4.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C32(H32A,H32B), C33(H33A,H33B), C40(H40A,H40B), C41(H41A,
 H41B), C14(H14A,H14B), C17(H17A,H17B), C6(H6A,H6B), C18(H18A,H18B), C11(H11A,
 H11B), C36(H36A,H36B), C10(H10A,H10B)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C44(H44A,H44B,H44C), C22(H22A,H22B,H22C), C1(H1A,H1B,H1C)
4.d Idealised tetrahedral OH refined as rotating group:
 O12(H12), O4(H4), O15(H15), O7(H7)
;
_shelx_res_checksum              80974
_shelx_hkl_checksum              90098
_olex2_date_sample_data_collection 2019-05-08
_olex2_date_sample_submission    2019-04-12
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id THP1957P1_130K
_olex2_submission_special_instructions 'No special instructions were received'