Energetic and rate effects of the trifluoromethyl group at C-2 and C-4 on the aliphatic Claisen rearrangement

Abstract

Supplementary Material Available: Cartesian coordinates and Z-matrices are provided for 1, 2, and 3 (10 pages). Ordering information is given on any current masthead page.

On the isolation of neat allylic fluorides

“…1 H NMR (500 MHz, CDCl 3 , 22 8C): d 7.45-7.43 (m, 2H, H o ), 7.39-7.31 (m, 3H, H m , H p ), 6.78 (d, 1H, 3 J H2-H3 = 16.0, C(3)H), 6.31 (dt, 1H, 3 J H2-H3 = 15.8, 3 J H2-H1 = 6.9, C(2)H), 5.00 (dd, 2H, 3 J H2-H1 = 6.9, 4 J H3-H1 = 0.8, C(1)H 2 ); data are in accord with literature values [25]. 13 (q,J = 42.5,C(O)O),137.33,137.32,135.6,129.0,127.1,120.3,114.7 (q,J = 285.8,CF 3 Geranyl chloride [27] (298 mg, 1.73 mmol) was added to Me 2 SO (5 mL) solution of Bu 4 NFÁ(H 2 O) 1.7 (660 mg, 93.0 wt.%, 2.10 mmol) in a scintillation vial in the glovebox.…”

“…), immediately producing visible smoke and turning into a deep purple solid. The solid was evacuated at RT for 3 h, heated closed under N 2 atmosphere at +90 8C for 25 (Fig. 4b).…”

Regioselective Asymmetric Allylic Alkylation Reaction of α‐Cyanoacet­ates Catalyzed by a Heterobimetallic Platina‐/Palladacycle

“…Oct‐1‐en‐3‐yl 2,2,2‐Trifluoroacetate (4): 34 A mixture of 1‐octen‐3‐ol (595.2 µL, 500.0 mg, 3.90 mmol, 1.00 equiv.) and 2,2,2‐trifluoroacetic anhydride (5.1 mL, 7.6 g, 36.18 mmol, 9.28 equiv.)…”

Combining oxidative addition and polymerization: A study towards the synthesis of macromonomers

“…= 112-114°C (12mbar) (lit. [2] 2-Trimethylsilylallyltrifluoroacetate (Id) was synthesized analogously to Ib, except that 2-trimethylsilylallyl alcohol was used instead of 2-phenylallyl alcohol. Yield: 13.8 g (58.9%); colorless liquid; b.p.…”