Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks

K. C. Nicolaou, C. K. Hwang, B. E. Marron, S. A. DeFrees, E. A. Couladouros, Y. Abe, P. J. Carroll, J. P. Snyder

研究成果: Article

122 引用 (Scopus)

抄録

A new reaction involving bridging of macrodithionolactones to bicyclic systems is described. A series of macrodiolides was prepared and converted to the requisite macrodithionolactones. The latter substrates were induced to undergo bridging across the macrocyclic ring by exposure to sodium naphthalenide, leading to stable bicyclic systems upon addition of methyl iodide. The mixed thioketals so obtained were converted to a number of saturated or unsaturated bicyclic or polycyclic systems by removal of the sulfurs. The stereochemistry of bridging follows the relative energy of the cis and trans products rather than the conformational preferences of the macrocycles. This is confirmed by MM2 calculations and X-ray crystal structure determinations. The unusual stereochemical course of some of the reported reactions, elucidated by X-ray, has been given a mechanistic basis by conformation searching coupled by energy evaluation by MM2 and PRDDO. Several new sets of MM2 parameters were evolved during this work.

元の言語English
ページ(範囲)3040-3054
ページ数15
ジャーナルJournal of the American Chemical Society
112
発行部数8
出版物ステータスPublished - 1990 4 11
外部発表Yes

Fingerprint

X-Rays
X rays
Stereochemistry
Sulfur
Conformations
Crystal structure
Sodium
Substrates
methyl iodide

ASJC Scopus subject areas

  • Chemistry(all)

これを引用

Nicolaou, K. C., Hwang, C. K., Marron, B. E., DeFrees, S. A., Couladouros, E. A., Abe, Y., ... Snyder, J. P. (1990). Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks. Journal of the American Chemical Society, 112(8), 3040-3054.

Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks. / Nicolaou, K. C.; Hwang, C. K.; Marron, B. E.; DeFrees, S. A.; Couladouros, E. A.; Abe, Y.; Carroll, P. J.; Snyder, J. P.

:: Journal of the American Chemical Society, 巻 112, 番号 8, 11.04.1990, p. 3040-3054.

研究成果: Article

Nicolaou, KC, Hwang, CK, Marron, BE, DeFrees, SA, Couladouros, EA, Abe, Y, Carroll, PJ & Snyder, JP 1990, 'Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks', Journal of the American Chemical Society, 巻. 112, 番号 8, pp. 3040-3054.
Nicolaou KC, Hwang CK, Marron BE, DeFrees SA, Couladouros EA, Abe Y その他. Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks. Journal of the American Chemical Society. 1990 4 11;112(8):3040-3054.
Nicolaou, K. C. ; Hwang, C. K. ; Marron, B. E. ; DeFrees, S. A. ; Couladouros, E. A. ; Abe, Y. ; Carroll, P. J. ; Snyder, J. P. / Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks. :: Journal of the American Chemical Society. 1990 ; 巻 112, 番号 8. pp. 3040-3054.
@article{ac710d3c7f75404fa3496575d00aaf44,
title = "Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks",
abstract = "A new reaction involving bridging of macrodithionolactones to bicyclic systems is described. A series of macrodiolides was prepared and converted to the requisite macrodithionolactones. The latter substrates were induced to undergo bridging across the macrocyclic ring by exposure to sodium naphthalenide, leading to stable bicyclic systems upon addition of methyl iodide. The mixed thioketals so obtained were converted to a number of saturated or unsaturated bicyclic or polycyclic systems by removal of the sulfurs. The stereochemistry of bridging follows the relative energy of the cis and trans products rather than the conformational preferences of the macrocycles. This is confirmed by MM2 calculations and X-ray crystal structure determinations. The unusual stereochemical course of some of the reported reactions, elucidated by X-ray, has been given a mechanistic basis by conformation searching coupled by energy evaluation by MM2 and PRDDO. Several new sets of MM2 parameters were evolved during this work.",
author = "Nicolaou, {K. C.} and Hwang, {C. K.} and Marron, {B. E.} and DeFrees, {S. A.} and Couladouros, {E. A.} and Y. Abe and Carroll, {P. J.} and Snyder, {J. P.}",
year = "1990",
month = "4",
day = "11",
language = "English",
volume = "112",
pages = "3040--3054",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks

AU - Nicolaou, K. C.

AU - Hwang, C. K.

AU - Marron, B. E.

AU - DeFrees, S. A.

AU - Couladouros, E. A.

AU - Abe, Y.

AU - Carroll, P. J.

AU - Snyder, J. P.

PY - 1990/4/11

Y1 - 1990/4/11

N2 - A new reaction involving bridging of macrodithionolactones to bicyclic systems is described. A series of macrodiolides was prepared and converted to the requisite macrodithionolactones. The latter substrates were induced to undergo bridging across the macrocyclic ring by exposure to sodium naphthalenide, leading to stable bicyclic systems upon addition of methyl iodide. The mixed thioketals so obtained were converted to a number of saturated or unsaturated bicyclic or polycyclic systems by removal of the sulfurs. The stereochemistry of bridging follows the relative energy of the cis and trans products rather than the conformational preferences of the macrocycles. This is confirmed by MM2 calculations and X-ray crystal structure determinations. The unusual stereochemical course of some of the reported reactions, elucidated by X-ray, has been given a mechanistic basis by conformation searching coupled by energy evaluation by MM2 and PRDDO. Several new sets of MM2 parameters were evolved during this work.

AB - A new reaction involving bridging of macrodithionolactones to bicyclic systems is described. A series of macrodiolides was prepared and converted to the requisite macrodithionolactones. The latter substrates were induced to undergo bridging across the macrocyclic ring by exposure to sodium naphthalenide, leading to stable bicyclic systems upon addition of methyl iodide. The mixed thioketals so obtained were converted to a number of saturated or unsaturated bicyclic or polycyclic systems by removal of the sulfurs. The stereochemistry of bridging follows the relative energy of the cis and trans products rather than the conformational preferences of the macrocycles. This is confirmed by MM2 calculations and X-ray crystal structure determinations. The unusual stereochemical course of some of the reported reactions, elucidated by X-ray, has been given a mechanistic basis by conformation searching coupled by energy evaluation by MM2 and PRDDO. Several new sets of MM2 parameters were evolved during this work.

UR - http://www.scopus.com/inward/record.url?scp=0025146271&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0025146271&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0025146271

VL - 112

SP - 3040

EP - 3054

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 8

ER -