Abstract
Total syntheses of (±)-21-oxogelsemine (3) and (±)-gelsemine (1) are described. Free radical cyclizations play important roles in constructing the tricyclic core (40 → 41) and oxindole (93 → 96) substructures of the target alkaloids, and an isomerization-cyclization strategy (101 → 102) was used to complete construction of the gelsemine cage. Observations made along the way include intramolecular 1,4- and 1,6-hydrogen atom transfers (64 → 65 and 40 → 47) and a free radical cyclization-fragmentation sequence (85 → 86 + 87). A retroaldol-aldol strategy for adjusting oxindole stereochemistry in gelsemine-like structures is also described (72 → 74 and 86 → 87).
| Original language | English |
|---|---|
| Pages (from-to) | 6226-6241 |
| Number of pages | 16 |
| Journal | Journal of the American Chemical Society |
| Volume | 119 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - 1997 Sep 10 |
| Externally published | Yes |
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Free radical cyclizations in alkaloid total synthesis : (±)-21- oxogelsemine and (±)-gelsemine. / Atarashi, Shogo; Choi, Joong Kwon; Ha, Deok-Chan; Hart, David J.; Kuzmich, Daniel; Lee, Chih Shone; Ramesh, Subban; Wu, Shung C.
In: Journal of the American Chemical Society, Vol. 119, No. 27, 10.09.1997, p. 6226-6241.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Free radical cyclizations in alkaloid total synthesis
T2 - (±)-21- oxogelsemine and (±)-gelsemine
AU - Atarashi, Shogo
AU - Choi, Joong Kwon
AU - Ha, Deok-Chan
AU - Hart, David J.
AU - Kuzmich, Daniel
AU - Lee, Chih Shone
AU - Ramesh, Subban
AU - Wu, Shung C.
PY - 1997/9/10
Y1 - 1997/9/10
N2 - Total syntheses of (±)-21-oxogelsemine (3) and (±)-gelsemine (1) are described. Free radical cyclizations play important roles in constructing the tricyclic core (40 → 41) and oxindole (93 → 96) substructures of the target alkaloids, and an isomerization-cyclization strategy (101 → 102) was used to complete construction of the gelsemine cage. Observations made along the way include intramolecular 1,4- and 1,6-hydrogen atom transfers (64 → 65 and 40 → 47) and a free radical cyclization-fragmentation sequence (85 → 86 + 87). A retroaldol-aldol strategy for adjusting oxindole stereochemistry in gelsemine-like structures is also described (72 → 74 and 86 → 87).
AB - Total syntheses of (±)-21-oxogelsemine (3) and (±)-gelsemine (1) are described. Free radical cyclizations play important roles in constructing the tricyclic core (40 → 41) and oxindole (93 → 96) substructures of the target alkaloids, and an isomerization-cyclization strategy (101 → 102) was used to complete construction of the gelsemine cage. Observations made along the way include intramolecular 1,4- and 1,6-hydrogen atom transfers (64 → 65 and 40 → 47) and a free radical cyclization-fragmentation sequence (85 → 86 + 87). A retroaldol-aldol strategy for adjusting oxindole stereochemistry in gelsemine-like structures is also described (72 → 74 and 86 → 87).
UR - http://www.scopus.com/inward/record.url?scp=0030742816&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0030742816&partnerID=8YFLogxK
U2 - 10.1021/ja970089h
DO - 10.1021/ja970089h
M3 - Article
AN - SCOPUS:0030742816
VL - 119
SP - 6226
EP - 6241
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 27
ER -