Table 1.

Attempted chemical oxidations^a

Substrate	Conditions	HPLC Yield of Oxygenation Products (%)b,c,d
		SM	C1	C7	C10	Polyoxygenation
5	SeO2, DCM, 40 °C	21	79 (57)e	–	–	–
12	SeO2, DCM, 40 °C	5	26 (22)	–	–	15
5	Pd/C (10 wt%), TPHP, 0 °C	7	–	3	44	46
12	Pd/C (10 wt%), TPHP, 0 °Cf	46	–	2	42	4
5	Cr(V) (1 equiv), MnO2 CF3C6H5, 15-crown-5, 80 °C	55	3	35g	–	6
5	Rh2(esp)2, T-HYDRO, 23 °C	2	8	21(10)	–	34
12	Rh2(esp)2, T-HYDRO, 23 °C	–	–	15	16	43

^aSee supporting information for reaction conditions and description of the product distribution.

^bApproximated by separating the products on UHPLC-MS and comparing ion count of the various oxidation products.

^cRemaining percent balance remaining were unidentified side products.

^dNumbers given in parentheses indicate isolated yields of the oxidized product.

^eProtection of 5 to as an N-acyl enamide results in oxidation at C-14.

^fShortened reaction time used to observe inherent regioselectivity without over oxidation.

^gOxidized product S14 was isolated.