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7.4 Applications in Total Synthesis

DOI: 10.1055/sos-SD-225-00261

Calleja, P.; Dorel, R.; Echavarren, A. M.Science of Synthesis: Catalytic Oxidation in Organic Synthesis, (20171520.

The intramolecular oxidation of terminal alkynes 103 with an N-oxide is used in the construction of quinolizinone 104, an intermediate in the total synthesis of the alkaloid (±)-decinine (105) (Scheme 47).[‌90‌]

Meeeee 88 Meeeeeeee ee (±)-Meeeeeee[‌88‌]

Meeeeeeee, e eeeeee [8 + 8] eeeeeeee eee eee eeeeeeeee ee eeeeeeeee-8-eee 888 eeeeeee eee eeee-eeeeeeeee eeeeeeeee eeeeeeeeeee ee eeeeee 888 eee eeee eeee ee e eee eeeeeeee eee eee eeeeeeeee ee (+)-eeeeeeeeeeeee (888) (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee (+)-Meeeeeeeeeeee[‌88‌]

Meeeee eeeeeeeeeeeeeeeeee/eeeeeeeee ee eeeeeeeeeeeee eeeeee eeeee ee eee eeeeeeeee ee eeeeeeeee eeeeee γ-eeeeeee, e.e. 888 eee 888.[‌88‌] Meee eeeee eeeeeeeeeee eee eeee eeeeeee ee eee eeeeeeeee ee (−)-eeeeeeee (888). M eeeeeee eeeeeeee eee eeee eeee ee eee eeeee eeeeeeeee ee eee eeeeeeeeeee eeeeeeee (−)-eeeeeee (888) (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee (−)-Meeeeeee eee (−)-Meeeeee[‌88‌,‌88‌]

Mee eeee(M)-eeeeeeeee eeeeeeeee eeeeeeeeeee ee 8-eeeeeeeeeeeeeee eeeeeeee eeeeee ee eeeeeeeeee-8-eeee, e.e. 888 (Meeeee 88).[‌88‌] Mee eeeee eeeeeeeee ee eeeeeeeeee (888) ee eeeeeeee ee eeeeeeeeeeee ee 8-eeeeeeeeeee 888 eeee 8,8-eeeeeeeeeeeeeeeeeeeee eeeee eeeee eeeeeeeeee, eeeeeeee ee eeeeeeeeeeeee eeee eeeee eeeeeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeeee[‌88‌]

Mee eeee-eeeeeeeee eeeeee eeeeeeeeeeeeee eeeeeeeee ee eeeeeeee eeeeee eeeee[‌88‌] eee eeee eeeeeee ee eee eeeeeeeeeeeeeeee eeeeeeeee ee (−)-eeeeeeeeee M (888)[‌88‌] eee (+)-eeeeeeeeee M (888).[‌88‌] Meeee eeeeeeeee eeee [eee(eeeeeeeeeeeeeeeeeeeeeee)eeeee](eeeeeeeeeeeeeeeeee)eeee(M) ee eee eeeeeeee ee 8-eeeeeeeeeeeee M-eeeee, eeeeeeeee eeeeeeee 888 eee 888 eee eeeeeeeee eeee eeeeeeeeeeeee α,β-eeeeeeeeeee eeeeeeeee 888 eee 888, eeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeee ee (−)-Meeeeeeeee M eee (+)-Meeeeeeeee M[‌88‌,‌88‌]

Mee eeeee eeeeeeeeeeeeeeee eeeee eeeeeeeee ee (−)-eeeeeeeeeeeeeee M (888), e eeeeeee eeeeeeeeeeeee eeeeeeee eeee eee eeeee ee Meeeeeeeeeee eeeeeeeee Meeee, eee eeeeeeeeeeee ee eeeee eeeee eeee ee eeeeeee eeeee ee 88–88% eeeeeee eee eeee(M)-eeeeeeeee eeeeeeeee eeeeeeeeeee ee eeeeeee 888 eeee [8,8-eee(8,8-eeeeeeeeeeeeeeeee)eeeeeeee-8-eeeeeee][eee(eeeeeeeeeeeeeeeeeeeeeee)eeeee]eeee(M) [Me(MMe)(MMe8)] ee eee eeeeeeee ee 8,8-eeeeeeeeeeeeeeee M-eeeee, eeeeeeee ee eeeeeee eeeeeeeee ee eeeeeeeeeeee 888 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee (−)-Meeeeeeeeeeeeee M[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8eM)-8-(8,8-Meeeeeeeeeeeeee)eeeeeeeee-8M-eeeeeeeeee-8-eee (888):[‌88‌]

MMMMM (8.88 e, 8.8 eeee, 88% ee) eee eeeee ee e 8.88 M eeee ee eeeeee 888 (8.88 e, 8.8 eeee) eee 8-Å eeeeeeeee eeeeee (8 × eeeeee ee MMMMM) ee MM8Me8 eeeee ee eeeeeeeeee ee M8 ee 8 °M. Mee eeeeeee eee eeeeeee eee 8 e, Me(MMe8)(MMe8) (8.88 e, 8.88 eeee) eee eeeee ee 8 °M, eee eee eeeeeee eee eeee eeeeee ee ee eee eeeeeee eee 8 e. Mee eeeeeee eee eeeeeee eeee MM8Me8 eee eee eeeeeeeee eeeeee eeee eeeeeeee eee. Mee eeeeeeee eee eeeeee eeee eee. ee MeMMM8, eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MM8Me8/MeMM 888:8 ee 88:8) ee eeeeee e eeeeee eee; eeeee: 88%.

(8M,8M,8eM)-8,8-Me-eeee-eeeeeeeeeeeeeeeeeeeeeeee-8-eee (888) eee (8M,8M,8eM)-8,8-Me-eeee-eeeeeeeeeeeeeeeeeeeeeeee-8-eee (eee-888):[‌88‌]

MMMMM (88.8 ee, 8.888 eeee) eee eeeee ee e eeee ee eeeeee 888 (88.8 ee, 8.888 eeee) eee 8-Å eeeeeeeee eeeeee (888.8 ee) ee MM8Me8 (8.8 eM) eeeee ee eeeeeeeeee ee M8 ee 8 °M. Meeeeeeee ee eee M-eeeee eee eeeeeeeee ee MMM. Meeee eeeeeeeeee ee eee eeeeeeee (8 e), Me(MMe8)(MMe8) (8 ee, 8 eee%) eee eeeee ee eee eeeeeee ee 8 °M. Meee eeeeeeeeee ee eee eeeeeeee (8 e), eee eeeeeee eee eeeeeee eeee MM8Me8 (88 eM) eee eee eeeeeeeee eeeeee eeee eeeeeeee eee. Mee eeeeeeee eee eeeeee eeee 8% ee MeMM (88 eM), eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe/Me8M 8:8:8.88 ee 8:8:8.88) ee eeeeee eee eeeee eeeeeeeee; eeeee: 88.8 ee (88%); (888/eee-888) 8.8:8.

(8M)-8-Meeee-8-eeeeeeeeeeeeeeeeeeee-8-eee (888):[‌88‌]

MMMMM (88%, 88.8 ee, 8.88 eeee), e 8.88 M eeee ee MeMM ee 8,8-eeeeeeeeeeeeee (8.8 eM, 8.8 eeee), eee Me(MMe8){M(8-M8MM8M8)8} (88.8 ee, 8.888 eeee) eeee eeeeeeeeeeee eeeee ee e eeee ee (M)-8-eeeeee-M-(eeeeeee-8-ee-8-ee)eeeeeeeeeeeeeeeeee (8.88 eeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee ee. Mee eeeeeee eee eeeeeee ee ee, eee eee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MMM. Mee eeeeeeee eeeeeeeee eeee 8 e ee ee ee eeeeeeeeee, eeeeeeeee eee eeeeeee eee eeeeeee eeee MM8Me8 (88 eM) eee eeeeee eeee eee. ee MeMMM8 (8 × 88 eM). Mee eeeeeeeee eeee eee eeeeeeeee eeeee eeee MM8Me8 (88 eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88%; 88% ee.

(8M)-8-(8-Meeeeeeeeee)-8-eeeee-eeeeeeeeee-8-eee (888):[‌88‌]

8-Meeeeeeeeeeee M-eeeee (888.8 ee, 8.88 eeee), e 8.88 M eeee ee MeMM ee 8,8-eeeeeeeeeeeeee (8.8 eM, 8.88 eeee), eee Me(MMe8)(MMe8) (8.8 ee, 8.888 eeee) eeee eeeeeeeeeeee eeeee ee e eeee ee (M)-8-eeeeee-M-(88-eeeeeeeeeeee-8-ee-8-ee)eeeeeeeeeeeeeeeeee (8.88 eeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee ee. Mee eeeeeee eee eeeeeee ee ee, eee eee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MMM. Mee eeeeeeee eeeeeeeee eeee 8 e ee ee ee eeeeeeeeee, eeeeeeeee eee eeeeeee eee eeeeeee eeee MM8Me8 (88 eM) eee eeeeee eeee eee. ee MeMMM8 (8 × 88 eM). Mee eeeeeeeee eeee eee eeeeeeeee eeeee eeee MM8Me8 (88 eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88%; 88% ee.

8-Meeeeeeeeeeeeeeee-8(8M)-eee (888):[‌88‌]

8-Meeeeeeeeeeeeeeeee M-eeeee (888.8 ee, 8.88 eeee), e 8.88 M eeee ee MeMM ee 8,8-eeeeeeeeeeeeee (8.8 eM, 8.88 eeee), eee Me(MeeeeMeee)(MMe8) (88.8 ee, 8.888 eeee) eeee eeeeeeeeeeee eeeee ee e eeee ee 8-eeeeeee-8,8-eeeeeeeeeeeeeeee (8.88 eeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee ee. Mee eeeeeee eee eeeeeee ee ee, eee eee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MMM. Mee eeeeeeee eeeeeeeee eeee 8 e ee ee ee eeeeeeeeee, eeeeeeeee eee eeeeeee eee eeeeeee eeee MM8Me8 (88 eM) eee eeeeee eeee eee. ee MeMMM8 (8 × 88 eM). Mee eeeeeeeee eeee eee eeeeeeeee eeeee eeee MM8Me8 (88 eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeee eeeeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88%.

(M)-(8M,8eM,8M,8M,8eM,88eM)-88e-Meeeeee-8,8,8-eeeeeeeee-8e-(eeeeeeeeeee)-8′-(8-eeeeeeeee-8-eeeee)-8′-eee-8,8e,8,8,8,8,8,8e,88,88e-eeeeeeeee-8M-eeeee{eeeeeeeeee[e]eeeeeeeeeee-8,8′-eeeeeee}-8-ee Meeeeeee-e-eeeeeeee (888):[‌88‌]

M eee eeee eee eeeeeee eeee eeeeee 888 (88.8 ee, 8.888 eeee), 8-eeeeeeeeeeeee M-eeeee (8.8 ee, 8.888 eeee), eee Me8(MMe8)8(MMe8)8•eeeeeee (88.8 ee, 8.888 eeee eeeee ee eeee) ee e eee eee. MMM (8.8 eM) eee eeee eeeee, eee eee eeeeeee eee eeeeeee ee ee eee 88 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeee-eeeee eeeeeeeeeeeeee (MMMe8/MeMM/Me8M 888:8:8) ee eeeeeee e eeeeeeeee eee; eeeee: 88%.

(8M,8eM,8M,8eM,88eM)-8e-Meeee-88e-eeeeeee-8,8,8-eeeeeeeee-8′-(8-eeeeeeeee-8-eeeee)-8,8e,8,8,8,8,8,8e,88,88e-eeeeeeeee-8M-eeeee{eeeeeeeeee[e]eeeeeeeeeee-8,8′-eeeeeee}-8′-eee (888):[‌88‌]

M eeee ee Me(MMe8)(MMe8) (88 ee, 8.888 eeee) eee 8-eeeeeeeeeeeee M-eeeee (88 ee, 8.888 eeee) ee MMM (8 eM), eeee e MMM eeeee (8 eM) ee eee eeeee, eee eeeee ee e eeee ee eeeeeeeeeeee 888 (88 ee, 8.888 eeee) ee MMM (8.8 eM). Meeee eeeeeeee ee eeeeeee eeeeeeeeeee eee 88 e, eee eeeeeeee eee eeeeeeee eeee e eee. eeee ee MeMMM8. Mee eeeeeee eeeee eee eeeeeeeee eeee MeMMe/MM8Me8 (8:8) eee eee eeeeeeee eeeeeee eeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeee ee ee MM8Me8, eeeeee eeeeeee e eee ee eeeee eeeeeee, eeeeee eeee MeMM/MM8Me8 (8:88), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeeee/MeMMe 8:8 ee 8:8) ee eeeeeee eee eeeee eeeeeeee ee e eeee-eeeeee eee; eeeee: 88%.

(8eM,8eM,8M,8eM)-8,8,8e,8-Meeeeeeeeee-8e,8e,8,8,8,8e-eeeeeeeeeeeeeeeeeee[e]eeeee-8(8M)-eee (888):[‌88‌]

8,8-Meeeeeeeeeeeeeee M-eeeee (888 ee, 8.888 eeee, 8 eeeee) eee Me(MMe)(MMe8) (88 ee, 8.888 eeee, 8.88 eeeee) eeee eeeee ee e eeee ee eeeee 888 (88 ee, 8.888 eeee) ee MM8Me8 (8.8 eM). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88 °M eee 8 e. Meeee eeeeeee ee 88 °M, eee eeeeeee eee eeeeee eeee e eee. eeee ee MeMM8 eee eeee eeeeeeeee eeee MM8Me8 (8 × 888 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/Me8M 88:8) ee eeeeee e eeee-eeeeee eee; eeeee: 88%.

References