Halomethyl metal compounds. XXXII. Insertion of phenyl (bromodichloromethyl)mercury-derived dichlorocarbene into carbon-hydrogen bonds. Alkanes and alkylbenzenes

Homologation Strategy for the Generation of 1-Chloroalkyl Radicals from Organoboranes

“…Purification by FC (pentane) afforded 51 as a colorless oil (205 mg, 53%) (57% GC yield). Spectral data were in accordance with literature data: , 1 H NMR (300 MHz, CDCl 3 ) δ 7.28–7.43 (m, 5H), 5.91 (d, J = 5.0 Hz, 1H), 3.47 (qd, J = 6.9, 5.1 Hz, 1H), 1.58 (d, J = 7.0 Hz, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 140.6, 128.6, 128.4, 127.8, 78.3, 50.4, 16.0. IR (neat) 3065, 3031, 2984, 2938, 1496, 1452, 1379, 1216, 797, 748, 725, 695 (s) cm –1 ; EI-LRMS (GC–MS) m / z 188 (5), 115 (9), 105 (100), 79 (11), 77 (9).…”

Novel insertion, rearrangement and addition products from dihalogenocarbene reactions with 5(10)-unsaturated steroids

“…19-Hydroxyandrost-4-ene-3,17-dione was converted by modification of the method described by Ueberwasser et al," uia estr-5( lO)-ene-3,17-dione 1, into the ketal alcohol 2a, which yielded 17~-(tert-butyldimethylsiloxy)-3,3-dirnethoxyestr-5 ( 10)-ene 2b (Scheme 1). Treatment of the 5( 10)-ene 2b with dibromocarbene, prepared from CHBr,-NaOH under phasetransfer catalysis (PTC) with cetyltrimethylammonium bromide (CTAB), gave multiple products but the expected addition product to the p face of the 5(10)-double bond3" was not isolated.…”

“…3,3-Ethylenedioxyestr-5 ( 10)-en-1 7-one 9 and 3,3,17,17-Bis-(ethylenedioxy)estr-5( 10)-ene 12.-The dione 1 (3.0 g), PTSA (1 25 mg) and ethylene glycol (42 cm3) were refluxed in benzene (160 cm3) in a Dean-Stark apparatus for 2 h. The organic layer was washed successively with aq. NaHCO, and water to give, after flash chromatography and elution with 20% EtOAc-LP, the diketall2 (2.55 g), m.p.…”

“…1 7~-(tert-Butyldimethylsiloxy)-3,3-ethylenedioxyestr-5 ( 10)ene 10.-A solution of the dione 1 (4 g), PTSA monohydrate (200 mg) and ethylene glycol (30 cm3) in benzene (320 cm3) was heated at 50°C for 1 h. The reaction mixture was washed successively with 6% aq. NaHCO, and water to give a residue (9), which was dissolved in MeOH (50 cm3) and NaBH, (2 g) was added slowly to the stirred solution for 1 h. The organic layer was separated and evaporated to give, after flash chromatography and elution with 20% EtOAc-LP, a residue (3.2 g), which was treated with imidazole (1.5 g), tertbutyldimethylsilyl chloride (3.0 g) and DMF (1 50 cm3) at 50 "C for 2 h. Water was added and the mixture was extracted with CH,Cl, to give the ketal 10 (3.76 g), m.p.…”

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, XLVII [1]. Einschiebungsreaktionen von phasentransferkatalytisch in situ erzeugten Dihalocarbenen in P-haltige Manganacycloalkane – Struktur und chemisches Verhalten der Reaktionsprodukte / Preparation and Properties of and Reactions with Metal-Containing Heterocycles, XLVII [1]. Insertion Reactions of Phase-Transfer-Catalytically in situ Generated Dihalocarbenes into P-Containing Manganacycloalkanes – Structure and Chemical

“…Zur in situ-Erzeugung von Dihalocarbenen eignen sich verschiedene Methoden [12][13][14][15][16][17][18]. Eine Möglich-keit besteht in der Eliminierung von Halogenwasserstoff aus Haloform durch starke Basen [14,18].…”